U.S. patent number 6,162,580 [Application Number 08/451,616] was granted by the patent office on 2000-12-19 for photosensitive polyimide precursor compositions processable by exposure to short wavelength light.
This patent grant is currently assigned to Asahi Kasei Kogyo Kabushiki Kaisha. Invention is credited to Yasuhiro Kataoka, Yoshio Matsuoka, Kanichi Yokota.
United States Patent |
6,162,580 |
Matsuoka , et al. |
December 19, 2000 |
Photosensitive polyimide precursor compositions processable by
exposure to short wavelength light
Abstract
The present invention provides photosensitive compositions which
comprise polyimide precursors having a chemical structure selected
from several specific chemical structures and/or specific amide
bond density and are adjusted so that the film obtained by applying
and drying the composition may exhibit a specific absorbance to
light. The polyimide film obtained by heat-curing the above
photosensitive composition exhibits excellent physical properties
and water resistance, and has high adhesive strength to epoxy
resins, inorganic materials and metals.
Inventors: |
Matsuoka; Yoshio (Fuji,
JP), Yokota; Kanichi (Fuji, JP), Kataoka;
Yasuhiro (Fuji, JP) |
Assignee: |
Asahi Kasei Kogyo Kabushiki
Kaisha (JP)
|
Family
ID: |
16677279 |
Appl.
No.: |
08/451,616 |
Filed: |
May 26, 1995 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
095783 |
Jul 21, 1993 |
|
|
|
|
Foreign Application Priority Data
|
|
|
|
|
Jul 22, 1992 [JP] |
|
|
4-215732 |
|
Current U.S.
Class: |
430/283.1;
430/325; 430/326 |
Current CPC
Class: |
G03F
7/0387 (20130101); H05K 1/0346 (20130101); H05K
3/4676 (20130101) |
Current International
Class: |
G03F
7/038 (20060101); G03C 001/73 () |
Field of
Search: |
;430/283,325,326,283.1 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
0254230 |
|
Jan 1988 |
|
EP |
|
0421195 |
|
Apr 1991 |
|
EP |
|
61-73740 |
|
Apr 1986 |
|
JP |
|
63-27828 |
|
Feb 1988 |
|
JP |
|
63-318549 |
|
Dec 1988 |
|
JP |
|
Other References
Adolfo R. Gutierrez et al., Maximizing Light Absorption at the
Bottom of a Film, Polymer Photochemistry 7 (1986) 517-521. .
Yamaoka et al., Polyfile vol. 27, No. 2 pp. 14-18 (1990) IEEE/SEMI
Advanced Semiconductor Manufacturing Conference, pp. 72-74 (1990)
(In Japanese). .
IEEE/SEM1 Advanced Semiconductor Manufacturing Conference, pp.
72-74 (1990). .
Journal of Applied Polymer Science, vol. 38, pp. 389-402 (1989).
.
Conference Preprints, Regional Technical Conference, Photopolymers
Principles--Processes and Materials, Oct. 28, 1991, pp. 333-342.
.
Polymeric Materials Science and Engineering, vol. 66, pp.
237-238..
|
Primary Examiner: Weiner; Laura
Attorney, Agent or Firm: Pennie & Edmonds LLP
Parent Case Text
This is a continuation, of application Ser. No. 08/095,783, filed
Jul. 21, 1993, now abandoned.
Claims
What is claimed is:
1. A process for forming a polyimide pattern which comprises the
steps of:
(1) selecting a Polymeric polyimide precursor which has an amide
bond density of from 1.5 to 2.42 mol/kg from the group consisting
of polymeric aromatic polyimide precursors which have a repeating
unit represented by the formula: ##STR55## wherein X is selected
from the group consisting of an unfluorinated aromatic ring bonded
to at least four substituents and an unfluorinated structure bonded
to at least four substituents that is composed of up to a total of
four aromatic rings linked to each other via bonds to at least one
type of linker selected from the group consisting of O, S, CO,
CH.sub.2, SO, SO.sub.2, and a single bond,
--COR and --COR' are substituents that occupy the ortho positions
of aromatic ring X with respect to the CONH substituent,
R and R' are OR.sub.1 wherein R.sub.1 is a group containing a
carbon--carbon double bond, and
Y is a structure bonded to at least two substituents, wherein an
aromatic ring bonded to the NH substituent, or an aromatic ring
adjacent to the aromatic ring bonded to the NH substituent via an O
linker, is substituted with an electron-withdrawing group lacking
hydrogen that is selected from the group consisting of an
alkylcarbonyl group, a nitrile group, and an alkylsulfone
group;
(2) applying a film of a photosensitive composition, which
comprises the polymeric polyimide precursor, a photopolymerization
initiator and a solvent, and which, at a thickness of 10 .mu.m,
exhibits an absorbance of 1.5 or less upon exposure to light of
wavelength of 365 nm, to an article capable of being covered by the
film;
(3) exposing the applied film to i-line light;
(4) removing unexposed areas of the film with a developing solution
to form a pattern; and
(5) heat-curing the resultant pattern.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel photosensitive composition
suitably used to manufacture semiconductor devices or multilayer
circuit boards in the field of electric and electronics.
Particularly, this invention relates to a photosensitive
composition applicable to a lithography process with a short
wavelength light source in order to obtain polyimide patterns after
annealing. Such a composition is becoming popular in the production
process of semiconductors.
2. Prior Art
Polyimides have been recognized as a material used in the field of
electronics for their high thermal and chemical stabilities, low
dielectric constant and excellent ability in planarization. These
polyimides have been widely used as materials for surface
protective layers, interlayer dielectrics of semiconductors and
insulating layers in multichip modules.
In order to obtain a desired pattern from ordinary polyimide
coatings, an indirect lithographic method wherein, for example, a
polyimide layer with patterned photoresist as an etching mask is
etched is employed. In this method, however, the process is
complicated. Moreover, the method has drawbacks such as the use of
harmful agents like hydrazine is required in the etching process
and the resolution of the polyimide pattern is reduced because of
the indirect lithographic method.
Accordingly, investigations into methods for direct pattern
formation of polyimides with photoreactive compounds having
polyimides or polyimide precursors have been conducted. In such
methods, the polyamic acid derivatives having double bonds linked
through ester bonds, amide bonds, acid ammonium salt and the like
are used. The polyamic acid derivatives can be used in the direct
photolithography process with photo initiators. The photosensitive
components are removed by heating to obtain thermally stable
polyimides (T. Yamaoka and T. Omote, "Polyfile", vol.27, no.2,
pp.14-18 (1990)). This technology is generally referred to as a
photosensitive polyimide technology.
A demand for accumulation of semiconductors such as IC, LSI, VLSI
has been gradually increasing. According to this demand, processing
technologies for fine materials has been expected. In one of the
technologies, the pattern formation of photoresists is conducted by
using short wavelength light such as i-line light of Hg lamp (365
nm wavelength) instead of ordinary G-line light (436 nm
wavelength), for which a high resolution can be expected. It has
been anticipated that all exposure apparatus will employ i-line
light at semiconductor munufacturing factories in the near
future.
On the other hand, in the case of conventional polyimide precursor
technology, the compositions to be used in this technology have
relatively high absorbance to i-line light. Further, the polyimide
precursor compositions are applied to be rather thick, that is, 12
.mu.m or more, in view of the shrinkage caused by removing the
photosensitive components during curing, because the polyimide
coating requires 6 .mu.m thick or more from the standpoint of the
physical properties. Therefore, conventional polyimide precursor
compositions do not allow i-line light to reach the bottom of its
coating. As a result, the bottom of the coating is not sufficiently
hardened by exposure and the pattern is washed away in development.
Consequently, i-line light is not suitable for the exposure light
source for obtaining a polyimide coating having more than a certain
thickness. (C. Schuoket, et al., "IEEE/SEMI Advanced Semiconductor
Manufacturing Conference", pp.72-74 (1990)).
When i-line light is used, a pattern formation of thin coatings
must be conducted several times to obtain sufficiently thick
polyimide coating, so that the accuracy of the resultant patterns
cannot be improved and the production process becomes complicated.
Therefore, i-line light exposure is not practical.
It has been known that a film of a fluorine-containing polyimide
precursor has high i-line light trasmittancy (T. Omote, T. Yamaoka
and K. Kosei, "Journal of Applied Polymer Sience", vol.38,
pp.389-402 (1989)). Polyimides, which are obtained by heat-curing
the precursors and contain fluorine in their main frame work, have
drawbacks in practical use. That is, they have a low adhesive
strength to other materials used with polyimides, such as base
inorganic materials, epoxy resins in coating layers and metals for
distributing wires when they are used for semiconductor devices and
multilayer circuit boards. A photosensitive polyimide precursor
composition, which can form patterns by means of i-line light and
is applicable to practical uses, has not yet been obtained.
SUMMARY OF THE INVENTION
The present invention provides a photosensitive polyimide
composition. From the composition, a polyimide film having more
than a certain thickness can be obtained by taking the process of
pattern formation by i-line exposure and a heat-cure. The
composition is applicable to practical uses.
A desirable pattern is formed by exposing the photosensitive
polyimide precursor composition to i-line light, which composition
comprises polyimide precursors having a chemical structure selected
from several specific chemical structures and/or specific amide
bond density and is adjusted so that the film obtained by applying
and drying the composition may exhibit specific absorbance. The
polyimide film obtained by heat-curing the above pattern exhibits
excellent physical properties and water resistance, and has high
adhesive strength to epoxy resins, inorganic materials and
metals.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides photosensitive compositions
comprising:
(A) an aromatic polyimide precursor (hereinafter referred to as a
polyimide precursor) having amide bond density of 1.5 mol/kg or
more and a repeating unit represented by the general formula (I):
##STR1## wherein X represents a tetravalent aromatic radical not
including a fluorine atom or a tetravalent organic radical having a
chemical structure in which 2 to 4 aromatic radicals are linked
through at least one type of bond selected from the group
consisting of a single bond, an ether bond, a thioether bond, a
carbonyl bond, a methylene bond, a sulfoxide bond and a sulfone
bond, and which does not include a fluorine atom; --COR and --COR'
groups take the ortho positions against --CONH group; R and R'
independently represent --OR.sub.1, --NHR.sub.2, --O--N.sup.+
R.sub.3 R.sub.4 R.sub.5 R.sub.6 or --OH groups, wherein R.sub.1 to
R.sub.3 represent organic radicals having olefinically unsaturated
bonds at least in part of the repeating units and may coexisit in
the repeating units; and R.sub.4 to R6 independently represent a
hydrogen atom or a hydrocarbon radical having 1 to 6 carbon atoms,
and R or R', contained at least in part of repeating units,
represents a residual group except for --OH; and Y represents a
divalent aromatic radical not including a fluorine atom or a
divalent organic radical having a chemical structure in which 2 to
6 aromatic radicals are linked through at least one type of bond
selected from the group consisting of a single bond, an ether bond,
a thioether bond, a carbonyl bond, a methylene bond, a
2,2-propylene bond, a sulfoxide bond and a sulfone bond, and which
does not include a fluorine atom,
(B) a photopolymerization initiator, and
(C) a solvent.
Moreover, the polyimide precursor of the photosensitive composition
satisfies at least one of the following conditions:
(i) amide bond density is 2.42 mol/kg or less,
(ii) X is a tetravalent radical wherein the aromatic radicals
connected with --CONH groups has a chemical structure in which the
aromatic radical is substituted with aprotic electron donating
group, and
(iii) Y is a divalent radical:
(iii-1) represented by the general formula (II): ##STR2## wherein
R.sub.7 represents an aliphatic hydrocarbon radical having 1 to 4
carbon atoms and n represents an integer of 0 to 3,
(iii-2) represented by the general formula (III): ##STR3## wherein
A represents --CH.sub.2 --, --CO--, --SO.sub.2 --, --O--, --S--, a
m-dioxyphenylene radical, a p-dioxyphenylene radical or a group
represented by the general formula (III-1): ##STR4## wherein B
represents --CH.sub.2 --, --CO--, --SO.sub.2 --, --O--, --S--, a
m-dioxyphenylene radical or a p-dioxyphenylene radical; and k
represents 0 or 1;
and m represents 0 or 1,
(iii-3) represented by the general formula (IV): ##STR5## wherein C
represents --SO.sub.2 --, --SO-- or --CO--, p represents 0, 1 or 2
and Z represents --O--, --CH.sub.2 -- or ##STR6## or (iii-4)
wherein an aromatic radical connected with --NH-- or an aromatic
radical adjacent to such an aromatic radical through an ether bond
has a chemical structure in which the aromatic radical is
substituted with aprotic electron attracting group.
A film, which is obtained by applying and drying the photosensitive
composition, has absorbance of 1.5 or less per 10 .mu.m thick at
365 nm wavelength light.
In the composition of the present invention, the polyimide
precursor used as component (A) is represented by the general
formula (I).
As for each aromatic radical contained in X and Y in the general
formula (I), groups having a benzene ring, a naphthalene ring or an
anthracene ring are preferred because the heat resistance of a
polyimide film obtained by heat-curing the photosensitive
composition having such radicals is high. As for the type of bond
between the aromatic radicals, one or more selected from the group
consisting of a single bond, an ether bond, a carbonyl bond and a
sulfone bond are preferred because of the the same reason as
mentioned above.
When the --COR or --COR' group in the general formula (I) is an
ester group represented by the general formula (V-1):
wherein R, is as defined above, it is necessary that the ester
group includes a group having an olefinically unsaturated bond such
as a 2-acryloyloxyethyloxycarbonyl radical, a
2-methacloyloxyethyloxycarbonyl radical, a
2-(1-acryloyloxy)propyloxycarbonyl radical,
2-(1-methacloyloxy)-propyloxycarbonyl radical, a
2-methacrylaminoethyloxycarbonyl radical, a
3-methacloyloxy-2-hydroxypropyloxycarbonyl radical and an
acrylaminomethyloxycarbonyl radical. Additionally, the ester group
may include a group not having an olefinically unsaturated bond
such as an ethoxycarbonyl radical, a methoxycarbonyl radical, a
2-methoxyethoxycarbonyl radical or a 2-ethoxyethoxy-carbonyl
radical.
When the --COR or --COR' group in the general formula (I) is an
amide group represented by the general formula (V-2):
wherein R.sub.2 is as defined above, it is necessary that the amide
group includes a group having an olefinically unsaturated bond such
as a N-(2-acryloyloxyethyl)aminocarbonyl radical and
N-(2-methacryloxyethyl)-aminocarbonyl radical. Additionally, the
amide group may include a group not having an olefinically
unsaturated bond such as a methylaminocarbonyl radical, a
ethylaminocarbonyl radical or a N-(2-ethoxyethyl)aminocarbonyl
radical.
When the --COR or --COR' group in the general formula (I) is an
ammonium salt of carboxylic acid represented by the general formula
(V-3):
wherein R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are as defined above,
it is necessary that the ammonium salt of carboxylic acid includes
a group having an olefinically unsaturated bond such as a
carboxylic acid 2-methacloyloxyethyl-trimethylammonium salt or a
carboxylic acid 2-acryloyloxyethyl-dimethylammonium salt.
Additionally, the ammonium salt of carboxylic acid may include a
group not having an olefinically unsaturated bond wherein all the
R.sub.3 to R.sub.6 are hydrogen atoms or hydrocarbon radicals.
When the --COR or --COR' group in the general formula (I) is a
carboxylic acid group, it is necessary that the groups mentioned in
the general fomulas (V-1), (V-2) or (V-3) also exist in the
repeating units of the polyimide precursor.
A polyimide precursor, which has a group selected from the groups
represented by the general formulas (V-1), (V-2) and a carboxylic
acid, and in which at least part of the repeating units has a
residual group except a carboxylic acid, is preferably used because
a coating thickness of the obtained photosensitive composition is
almost unchanged during development and the polyimide pattern has
good reproducibility from the photomask and has high resolution. A
polyimide precursor, which has only the ester group represented by
the general formula (V-1), is more preferably used because the
obtained photosensitive composition has good storage stability and
wide process margin for patterning, that is, the pattern is almost
unchanged depending on a fluctuation of process conditions such as
a process period in patterning, temperature.
In the composition of the present invention, the polyimide
precursor used as component (A) should have amide bond density of
1.5 mol/kg or more. The amide bond density means a value obtained
by dividing 2000 by a molecular weight of the repeating unit of the
polyimide precursor or a value obtained by dividing 2000 by an
average molecular weight, which is calculated from a molecular
weight of each repeating unit and a molar ratio of each repeating
unit if the polyimide precursor has several kinds of the repeating
unit. The amide bond density is a parameter representing a mole
value of an amide group present in 1 kg of the polyimide precursor.
When the amide bond density is lower than 1.5 mol/kg, heat
resistance is considerably degraded.
The polyimide precursor used represented by the general formula (I)
is well-known as a precursor of a heat resistant macromolecule and
is produced by known methods described by, for example, R. Rubner
et al. ("Photographic Science Engineering", vol.23, p.303 (1979)),
M. T. Pottiger et al. ("The 38th Electronic Components Conference",
p.315 (1988)), L. Minnema et al. ("Polymer Engineering and
Science". vol.28, no.12, p.815 (1988)) and Davis et al. ("Chemical
& Engineering News; Sep. 26, 1983", p.23). Additionally, the
polyimide precursor can be also produced by the methods described
in U.S. Pat. Nos. 4,645,823 and 4,243,743, European Patent
Unexamined Publication No. 421,195 and Japanese Patent Application
Laid-Open No. 4226/1991.
According to these methods, the polyimide precursor is produced by
using an aromatic tetracarboxylic dianhydride (hereinafter referred
to as ATC dianhydride) represented by the general formula (VI), an
aromatic diamino compound represented by the general formula (VII)
as a part of raw materials. ##STR7##
wherein X is as defined above.
wherein Y is as defined above.
When a compound having a group containing a fluorine atom such as a
fluorine group and a trifluoromethyl group is used as a raw
material for the polyimide precursor of the present invention, a
fluorine-containing polyimide obtained by heat-curing the
photosensitive composition is not applicable to practical uses
because of its low adhesive strength to other material.
It is necessary to use a polyimide precursor satisfying at least
one or more specific conditions in order to obtain the
photosensitive composition of the present invention. Specific
conditions mean the conditions (i) to (iii-4) mentioned above. As
long as the photosensitive composition of the present invention
satisfies the other conditions described in the above, conditions
(i) to (iii-4) can be used without any restriction.
The amide bond density must be at least 1.5 mol/kg as mentioned
above. When the amide bond density is 2.42 mol/kg or less and the
condition of polyimide precursor described in (A) is satisfied, the
composition of the present invention can be obtained regardless of
the structure of the polyimide precursor and i-line absorbance of
the obtained polymer coating becomes lower and water resistance of
the heat-cured film becomes higher with a decrease in the amide
bond density. The polyimide precursor having amide bond density of
from 2.0 to 2.42 mol/kg is preferred because the obtained polyimide
film has higher mechanical strength and heat resistance.
For the preparation of the polyimide precursor satisfying condition
(ii), an ATC dianhydride is used, wherein the aromatic radical
having a carboxylic anhydride group has a chemical structure in
which the aromatic radical is substituted with an aprotic electron
donating group (hereinafter referred to as ATC dianhydride under
condition (ii)'). Herein, the aprotic group may not be a group
having active hydrogen such as an alcohol, an amine and a
carboxylic acid. The electron donating group indicates a
substituting group, whose value of .sigma.p or .sigma.m is minus in
Hammett's rule. The rule and value are widely known, for example,
Section 365 of "Kagaku Binran Kisohen II" edited by Nippon Kagaku
Kai and published by Maruzen Company, Limited in 1984.
Representative examples of the aprotic electron donating groups
include a dialkylamino group, an alkoxy group, an aryloxy group, a
trialkylsilyl group, a benzyl group and an alkyl group.
Representative examples of the ATC dianhydrides under condition
(ii)' include 3,3',4,4'-diphenylether tetracarboxylic dianhydride,
1,4-dimetoxy-2,3,5,6-benzene tetracarboxylic dianhydride,
1,4-ditrimethylsilyl-2,3,5,6-benzene tetracarboxylic dianhydride,
1,4-bis-(3,4-dicarboxylphenoxy)benzene dianhydride,
1,3-bis(3,4-dicarboxylphenoxy)benzene dianhydride,
3,31,4,4'-diphenyl-methane tetracarboxylic dianhydride,
bis(3,4-dicarboxyl-phenoxy)dimethylsilane dianhydride,
bis(3,4-dicarboxyl-phenoxy)methylamine dianhydride,
4,4'-bis(3,4-dicarboxyl-phenoxy)biphenyl dianhydride and
4,4'-bis(3,4-dicarboxyl-phonoxy)diphenylsulfone dianhydride.
In the present invention, as long as the absorbance of a coating
obtained from the photosensitive composition is 1.5 or less per 10
.mu.m thick at 365 nm wavelength, the ATC dianhydride represented
by the general formula (VI) other than the one under condition
(ii)' can be used: (1) by mixing with the ATC dianhydride under
condition (ii)'; (2) by combining with the specific aromatic
diamino compound mentioned below; or (3) if an aromatic polyimide
precursor having specific amide bond density is obtained.
Representative examples of these compounds include pyromellitic
dianhydride, 2,3,5,6-naphthalene tetracarboxylic dianhydride,
3,3',4,4'-benzophenone tetracarboxylic dianhydride,
3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,5,6-pyridine
tetracarboxylic dianhydride, 2,3,6,7-quinoline tetracarboxylic
dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride,
3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride and
3,3',4,4'-diphenylsulfoxide tetracarboxylic dianhydride. In
addition, they include 1,2,8,9-anthracene tetracarboxylic
dianhydride, 1,4-bis(3,4-dicarboxylphenylsulfonyl)benzene
dianhydride, 1,4-bis(3,4-dicarboxylphenylthio)benzene dianhydride,
3,3",4,4"-terphenyl tetracarboxylic dianhydride,
4-phenyl-benzophenone-3,3,4,4"-tetracarboxylic dianhydride,
1,4-bis-(3,4-dicarboxylbenzoyl)-benzene dianhydride,
3,3'",4,4'"-quaterphenyl tetracarboxylic dianhydride,
4,4'-bis(3,4-dicarboxylphenoxy)-benzophenone dianhydride and
4,4'-bis(3,4-dicarboxylphenoxy)-diphenylsufoxide dianhydride.
For the preparation of the aromatic polyimide precursor satisfying
condition (iii-1), an aromatic diamino compound wherein Y is a
divalent group represented by the general formula (II) (hereinafter
referred to as an aromatic diamino compound under condition
(iii-1)') is used. Representative examples of the aromatic diamino
compounds include methaphenylenediamine, 3,5-diaminotoluene,
2,4-diaminotoluene and 2,4-diaminomesitylene.
For the preparation of the aromatic polyimide precursor satisfying
condition (iii-2), an aromatic diamino compound wherein Y is a
divalent group represented by the general formula (III)
(hereinafter referred to as an aromatic diamino compound under
condition (iii-2)') is used. Representative examples of the
aromatic diamino compounds include 4,4'-bis(3-aminophenoxy)bipenyl,
1,3-bis(3-aminophenoxy)-benzene, 3,3'-diaminobiphenyl,
3,3'-diaminodiphenylether, 3,3'-diaminodiphenylsulfone,
3,3'-diamino-benzophenone, 3,3'-diaminodiphenylmethane,
3,3'-diamino-diphenylsulfide,
4,41-bis(3-aminophenoxy)diphenylsulfone,
4,4'-bis(3-aminophenoxy)diphenylmethane,
4,4'-bis(3-aminophenoxy)diphenylether and
4,4'-bis(3-aminophenoxy)-diphenylsulfide.
For the preparation of the aromatic polyimide precursor satisfying
condition (iii-3), an aromatic diamino compound wherein Y is a
divalent group represented by the general formula (IV) (hereinafter
referred to as an aromatic diamino compound under condition
(iii-3)') is used. Representative examples of the aromatic diamino
compounds include 4,4'-diaminodiphenylsulfone,
4,4'-diamino-benzohenone, 4,4'-diaminodiphenylsulfoxide,
4,4'-bis(4-aminophenoxy)-diphenylsulfone,
4,4'-bis(4-aminophenoxy)diphenylsulfoxide and
4,4'-bis(4-aminophenoxy)benzophenone.
For the preparation of the aromatic polyimide precursor satisfying
condition (iii-4), an aromatic diamino compound wherein an aromatic
radical having an amino group or an aromatic radical adjacent to
such an aromatic radical linked through an ether bond has a
chemical structure in which the aromatic radical is substituted
with an aprotic electron attracting group (hereinafter referred to
as an aromatic diamino compound under condition (iii-4)') is used.
The electron attracting group used herein indicates a substituting
group having 0.2 or more of .delta.p or .delta.m value mentioned
above. Aprotic electron attracting groups include an acyloxy group,
an acylamino group, a halogen group, an alkylaminocarbonyl group,
an alkoxycarbonyl group, an alkylcarbonyl group, a nitrile group,
an alkylsulfone group, a nitro group and an alkoxysulfone group.
Representative examples of the aromatic amino compounds under
condition (iii-4)' include 4,4'-diaminobenzophenone,
4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone,
4,4'-diaminodiphenylsulfoxide,
bis[4-(4-aminophenoxy)phenyl]sulfone,
4,4'-bis[4-(4-aminophenoxy)-phenylsulfonyl]diphenylether,
bis[4-(3-aminophenoxy)-phenyl]sulfone,
4,4'-bis(4-aminophenoxy)benzophenone,
1,4-bis(4aminophenylsulfonyl)benzene,
1,4-bis[4-(4-aminophenoxy)phenylsulf onyl]benzene,
4,4'-bis(4-aminophenyl-sulfonyl)diphenylether,
3,5-diaminoethylbenzoate, 2,4-diaminobenzamide,
3,5-diaminobenzophenone,
4-dimethylamino-3',5'-diamino-benzophenone,
3,5-diamino(2-methacryloxyethyl)benzoate, 3,5-diaminoacetanilide,
4-chloro-m-phenylenediamine, 3,5-diaminobenzonitrile and
5-nitro-m-phenylenediamine.
In the present invention, as long as the absorbance of a coating
obtained from the photosensitive composition is 1.5 or less per 10
.mu.m thick at 365 nm wavelength, the aromatic diamino compound
represented by the general formula (VII) other than the specific
aromatic diamino compound mentioned above can be used: (1) by
mixing with the specific aromatic diamino compound mentioned above;
(2) by combining with the ATC dianhydride under condition (ii)'; or
(3) if an aromatic polyimide precursor having specific amide bond
density is obtained. Representative examples of the aromatic
diamino compounds, include 4,4'-diaminodiphenylether,
4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylether,
1,4-phenylenediamine, 2,7-naphthalenediamine,
3,3'-dimethyl-4,4'-diaminobiphenyl,
3,3'-dimethoxy-4,4'-diaminobiphenyl,
3,3'-dichloro-4,4'-diaminobiphenyl,
1,4-bis(4-aminophenoxy)-benzene, 1,3-bis(4-aminophenoxy)benzene,
5,8-diaminoquinoline, 4,4'-bis(4-aminophenoxy)biphenyl,
4,4'-diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]ether,
1,4-bis(4-aminophenyl)-benzene, 9,10-bis(4-aminophenyl)anthracene,
4,4'-bis(4-aminophenoxy)diphenylmethane,
4,4'-bis(4-aminophenoxy)-diphenyl sulfide,
bis[2-(4-aminophenyl)-benzothiazolyl]ether,
bis[2-(4-aminophenyl)-benzimidazolyl]sulfoxide,
bis[2-(4-aminophenyl)-benzoxazolyl],
4-(4-aminophenylsulfonyl)-4'-aminobiphenyl,
4,4'-bis(4-aminophenyl)diphenylether and
1,4-di-(4-aminobenzoyloxy)butane. Of the aromatic diamino compounds
under conditions (iii-1)' to (iii-4)', the aromatic diamino
compounds under conditions (iii-2)' and (iii-3)' are preferred
because polyimides obtained by heat-curing the photosensitive
composition achieve high heat resistance, tensile strength and
water resistance when they are used. Since the heat resistance,
tensile strength and water resistance of the polyimides are further
improved, of the aromatic diamino compounds under condition
(iii-2)', bis[4-(3-aminophenoxy)-phenyl]sulfone,
3,3-diaminodiphenylsulfone, 1,3-bis(3-aminophenoxy)benzene and
4,4'-bis(3-aminophenoxy)biphenyl are more preferred; and, of the
aromatic diamino compounds under condition (iii-3)',
bis[4-(4-aminophenoxy)pnenyl]sulfone, 4,4'-diaminobenzophenone,
4,4'-bis[4-(4-aminophenoxy)phenoxy]-diphenylsulfone,
4,4'-diaminodiphenylsulfoxide and 4,4'-aiaminodiphenylsulfone are
more preferred.
Representative examples of component (B) used as a
photopolymerization initiator include benzophenone derivatives such
as benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4'-methyl
diphenyl ketone, dibenzyl ketone and fluorenone; acetophenone
derivatives such as 2,2'-diethoxyacetophenone,
1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl
propiophenone; thioxanthaone derivatives such as thioxanthone,
2-methylthioxanthone, 2-isopropyl thioxanthone and diethyl
thioxanthone; benzyl derivatives such as benzyl, benzyl dimethyl
ketal and benzyl-p-methoxyethyl acetal; benzoin derivatives such as
benzoin and benzoin methylether; azido derivatives such as
2,6-di(4-azidobenzylidene)-4-methylcyclohexanone and
2,6-di(4-azidobenzylidene)cyclohexanone; and oxime derivatives such
as 1-phenyl-1,2-butadione-2-(O-methoxycarbonyl)oxime,
1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime,
1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime,
1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime,
1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime and
1-phenyl-3-ethoxy-propanetrione-2-(O-benzoyl)oxime. Of these, oxime
derivatives are preferred for its high photosensitivity. The amount
of the photopolymerization initiator is preferably in the range of
from 1 to 15 parts by weight per 100 parts by weight of polyimide
precursor.
Representative examples of component (C) used as solvents include
N,N'-dimethylformamide, N-methylpyrrolidone,
N-acetyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol
dimethylether, cyclopentanone, .gamma.-butyrolactone and
.alpha.-acetyl-.gamma.-butyrolactone. They may be used individually
or in combination. These solvents may be employed in the range of
from 100 to 400 parts by weight per 100 parts by weight of the
polyimide precursor according to thickness of the films or
viscosity of the composition.
The compounds having a reactive carbon--carbon double bond can be
used in addition to the above-mentioned components (A) to (C) to
improve photosensitivity of the present composition, if desired.
Representative examples of such compounds include
1,6-hexandioldiacrylate, neopentyl glycol diacrylate, ethylene
glycol diacrylate, polyethylene glycol diacrylate having 2 to 20 of
repeating units, pentaerythritol diacrylate, dipentaerythritol
hexacrylate, trimethylolpropane triacrylate, tetramethylolmethane
tetraacrylate, methylene bisacrylamide, N-methylolacrylamide, and
corresponding methacrylate and methacrylamide to the
above-mentioned compounds. These compounds may be employed in the
range of from 1 to 30 parts by weight per 100 parts by weight of
the polyimide precursor.
Sensitizers can be used to improve photosensitivity of the present
composition, if desired. Representative examples of the sensitizers
include Michler's ketone, 4,4'-bis(diethylamino)benzophenone,
2,5-bis(4-diethylaminobenzylidene)cyclopentanone,
2,6-bis(4-diethylaminobenzylidene)cyclohexanone,
2,6-bis(4-dimethylaminobenzylidene)-4-methylcyclohexanone,
2,6-bis(4-diethylaminobenzylidene)-4-methylcyclohexanone,
4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)-chalcone,
2-(4'-dimethylamino cinnamylidene)indanone, 2-(4'-dimethylamino
benzylidene)indanone, 2-(p-4'-dimethylaminobiphenyl)-benzothiazole,
1,3-bis(4-dimethylaminobenzylidene)acetone,
1,3-bis(4-diethylaminobenzylidene)-acitone,
3,3'-carbonyl-bis(7-diethylamino coumarin),
3-acetyl-7-dimethylamino coumarin, 3-ethoxycarbonyl-7-dimethylamino
coumarin, 3-benzyloxycarbonyl-7-dimethylamino coumarin,
3-methoxycarbonyl-7-diethylamino coumarin,
3-ethoxycarbonyl-7-diethylamino coumarin,
N-ethyl-N-phenyl-ethanolamine, N-phenyldiethanolamine,
N-p-tolyldiethanolamine, N-phenyl-ethanolamine,
4-morpholino-benzophenone, 4-dimethylamino isoamylbenzoate,
4-diethylamino isoamylbenzoate, 2-mercapto-benzimidazole,
1-phenyl-5-mercapto-1,2,3,4-tetrazole, 2-mercapto-benzothiazole,
2-(p-dimethylaminostyryl)-benzoxazole,
2-(p-dimethylaminostyryl)-benzthiazole,
2-(p-dimethylaminostyryl)naphtho(1,2-d)-thiazole and
2-(p-dimethylaminobenzoyl)styrene. Of these, a combination of
compounds having a mercaptho group and compounds having a
dialkylaminophenyl group is preferred for its sensitivity. They may
be used individually or in combination of two to five compounds.
The amount of the sensitizer is preferably in the range of from 0.1
to 10 parts by weight per 100 parts by weight of the polyimide
precursor.
An adhesion promoter can be added to the composition of the present
invention to improve an adhesive strength, if desired.
Representative examples of the promoter include
.gamma.-aminopropyltrimethoxysilane,
N-(.beta.-aminoethyl)-.gamma.-aminopropylmethyldimethoxysilane,
1-glycidoxypropylmethyldimethoxysilane,
.gamma.-glycidoxypropylmethyldiethoxysilane,
.gamma.-mercapthopropylmethyldimethoxysilane,
3-methacryloxypropyldimethoxymethylsilane,
3-methacryloxypropyltrimethoxysilane,
dimethoxymethyl-3-piperidinopropylsilane,
diethyoxy-3-glycidoxypropylmethylsilane,
N-(3-diethoxymethylsilylpropyl)succinimide,
N-[3-(triethoxysilyl)propyl]phthalamic acid,
benzophenone-3,3'-bis(3-triethoxysilylpropylaminocarbonyl)-4,4'-dicarboxyl
ic acid and
benzene-1,4-bis(3-triethoxysilylpropylaminocarbonyl)-2,5-dicarboxylic
acid. The amount of the promoter is preferably in the range of from
0.5 to 10 parts by weight per 100 parts by weight of the polyimide
precursor.
A polymerization inhibitor can be added to the composition of the
present invention to improve stability of sensitivity and viscosity
of the composition solution in preservation, if desired.
Representative examples of the inhibitor include hydroquinone,
N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine,
N-phenylnaphthylamine, ethylenediamine tetraacetic acid,
1,2-cyclohexanediamine tetraacetic acid, 2',2'-diethyletherdiamine
tetraacetic acid, 2,6-di-tert-butyl-p-methylphenol,
5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol,
2-nitroso-1-naphtol,
2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol,
N-nitroso-N-phenylhydroxylamine ammonium salt,
N-nitroso-N-(1-naphthyl)-hydroxylamine ammonium salt and
bis(4-hydroxy-3,5-tertbutylphenyl)methane. The amount of the
inhibitor is preferably in the range of from 0.005 to 5 parts by
weight per 100 parts by weight of the polyimide precursor.
In the present invention, it is necessary that the absorbance at
365 nm wavelength (i-line) light of a 10 .mu.m thick dried coating
obtained from a polyimide precursor composition be 1.5 or less to
form a pattern on the film with i-line wavelength light. When the
absorbance is over 1.5, the light intensity is not sufficient at
the bottom of the film so that a satisfactory pattern is not
formed.
The above-mentioned absorbance can be adjusted by the amounts of
essential components (A) to (C) and other additives.
The photosensitive compositions of the present invention can be
produced by mixing the above-mentioned components (A) to (C) and
others. And, from the thus obtained composition, a polyimide film
can be obtained by taking steps as descirbed below.
The compositions of the present invention are applied on a
substrate by using, for instance, a spin-coater, a bar-coater, a
blade-coater, a curtain-coater, screen printing press and a
spray-coater.
The resultant coating can be dried by air-drying, heating in an
oven or on a hot plate, and vacuum drying.
The dried coating should be exposed with a ultraviolet ray, etc. as
a light source by using an exposure equipment such as a contact
aligner, a mirror projection aligner and a stepper. Of these, a
stepper and i-line as a light source are preferred for its high
resolution and easy handling.
The irradiated film can be developed by conventional methods for
developing photoresist such as a spin-spray method, a puddle method
and a dipping method with a supersonic wave. Preferably, a
developing solution is a combination of good and poor solvents to
the above-mentioned polyimide precursor. Representative examples of
good solvents include N-methylpyrrolidone, N-acethyl-2-pyrrolidone,
N,N'-dimethylacetamide, cyclopentanone, cyclohexanone,
.gamma.-butyrolactone, .alpha.-acethyl-.gamma.-butyrolactone.
Representative examples of poor solvents include toluene, xylene,
methyl alcohol, ethyl alcohol, isopropyl alcohol and water. The
ratio of both solvents is adjusted according to the solubility of
the polyimide precursor. They may be used in combination. If
necessary, when the polyimide precursor contains carboxylic acids,
the aqueous solution of organic bases such as cholinehydroxide and
tetramethylammonium hydroxide can be used as a developing solution,
or used by being added to the above-mentioned organic solvents
according to the solubility of the polyimide precursor.
The resultant patterned film are heat-cured to obtain a polyimide
film as a result of evaporation of volatile components. This
process can be carried out by using a hot plate, an oven, and an
oven capable of storing temperature program. Air, nitrogen and
inert gas such as argon may be used as an atmosphere in heat-curing
the patterned film.
DESCRIPTION OF PREFERRED EMBODIMENT
The present invention is now described in more detail by referring
to Examples, but the scope thereof is not restricted by them.
Each characteristic of the compositions in Examples and Comparative
Examples was determined as follows:
(1) Amide bond density
Amide bond density [C] is calculated according to the equation
below. ##EQU1## In the equation, [M]C represents the molecular
weight of a tetracarboxylic acid unit, and it is calculated by
subtracting 32 (=the atomic weight of oxygen atom.times.2) from the
molecular weight of an ATC dianhydride used as a starting material.
When two or more of ATC dianhydrides are employed, their average
molecular weight is used for the calculation. [M].sub.A represents
the molecular weight of an aromatic diamine unit, and it is
calculated by subtracting 2 (=the atomic weight of hydrogen
atom.times.2) from the molecular weight of an aromatic diamino
compound used as a starting material. When two or more of the
aromatic diamino compounds are employed, their average molecular
weight is used for the calculation. [M].sub.S represents the total
amount of substituting groups R and R' which bind to aromatic rings
through carbonyl group in the polyimide precursor, and it is
calculated by doubling the average molecular weight of R and R'
radicals. The atomic weights used in the above calculation are 12
for carbon, 14 for nitrogen, 16 for oxygen, 32 for solfur and 1 for
hydrogen, respectively. A numerator 2000 is the coefficient to
calculate the mole value of amide bonds per 1 kg of the polyimide
precursor.
(2) Absorbance of polyimide precursor
N-methylpyrrolidone solution of polyimide precursor is applied on a
1 mm thick quartz plate using a spin-coater and dried in an oven at
80.degree. C. for 40 min. to form a 10 .mu.m thick polyimide
precursor coating. Then, its absorbance (referred to hereinafter as
precursor absorbance) at 365 nm is measured by ultraviolet
spectroscope UV-240 type (manufactured by Shimazu Corporation) and
is calculated according to the following equation:
(wherein I.sub.0 represents incident light intensity; I represents
transmitted light intensity through a film.)
(3) Absorbance of photosensitive composition coating
A photosensitive composition is applied on a 1 mm thick quartz
plate using a spin-coater and dried in an oven at 80.degree. C. for
40 min. to form a 10 .mu.m thick photosensitive composition
coating. Then, its absorbance (referred to hereinafter as coating
absorbance) is measured by the same method as (2).
(4) Viscosity number of polyimide precursor
Viscosity number (.eta.sp/c) of polyimide precursor in
N-methylpyrrolidone (1 g/dl) is measured by Auto Viscometer AVL-2C
(manufactured by San Denshi Ind. Co., Ltd.) at 30.degree. C.
(5) Viscosity of photosensitive composition
Viscosity of the photosensitive composition solution is measured by
an E type viscometer (manufactured by Tokyo Keiki Co., Ltd.:
VISCONIC-EMD type) at 23.degree. C.
(6) Tensile strength and elongation of polyimide film
In each Example, the general procedure is repeated except that the
obtained film on the wafer is exposed without a photomask and is
not developed. The resultant polyimide film is peeled from the
wafer, and its tensile strength and elongation are measured
according to ASTM D-882-88.
(7) Pull test
Adhesive strength between a polyimide film and a silicon wafer is
measured as follows. After the photosensitive composition on the
wafer is heat-cured, a pin having a diameter of 2 mm is attached to
the polyimide film with epoxy resin adhesive (AralditeO.RTM.
standard manufactured by Showa Highpolymer Co., Ltd.). The obtained
sample is subjected to a pull test using a pull tester
(manufactured by Quad Company Group, SEBASTIAN 5 type).
The standard of judgement:
______________________________________ Pulling stress (kg/mm.sup.2)
Adhesive strength ______________________________________ 7 or less
Good 6 to 5 Usable Less than 5 Poor
______________________________________
(8) Water resistance test
After the photosensitive composition on the wafer is heat-cured, it
is kept in boiling water for 48 hrs. and dried in an oven at
50.degree. C. for 2 hrs. Then, it is subjected to the
above-mentioned pull test.
The standard of judgement:
______________________________________ Pulling stress (kg/mm.sup.2)
Water resistance ______________________________________ 7 or more
Good 6 to 3 Usable Less than 3 Poor
______________________________________
(9) Raw material
ATC dianhydrides used in Preparations are represented by the
following symbols. The structural formulas shown below represent X
in the general formula (VI).
X-1: 3,3',4,4'-benzophenone tetracarboxylic dianhydride ##STR8##
X-2: 3,3',4,4'-diphenylether tetracarboxylic dianhydride ##STR9##
X-3: 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride
##STR10## X-4: 3,3"4,4"-terphenyltetracarboxylic dianhydride
##STR11## X-5: 1,4-bis(3,4-dicarboxylbenzoyl)benzene dianhydride
##STR12## X-6: 4,4'-bis(3,4-dicarboxylphenoxy)bipheny dianhydride
##STR13## X-7: 4,4'-bis(3,4-dicarboxylphenoxy)diphenyl sulfone
dianhydride ##STR14## X-8: 3,3',4,4'-biphenyl tetracarboxylic
dianydride ##STR15## X-9: 1,4-dimetoxy-2,3,5,6-benzene
tetracarboxylic dianhydride ##STR16## X-10:
3,3',4,4'-diphenylmethane tetracarboxylic dianhydride ##STR17##
X-11: pyromellitic dianhydride ##STR18##
Aromatic diamino compounds used in the Preparations are represented
by the following symbols. The structural formulas shown below
represent Y in the general formula (VII).
Y-1: 4,4'-bis(4-aminophenoxy)biphenyl ##STR19## Y-2:
9,10-bis(4-aminophenyl)anthracene ##STR20## Y-3:
bis[4-(4-aminophenoxy)phenyl]ether ##STR21## Y-4:
bis[4-(3-aminophenoxy)phenyl]sulfone ##STR22## Y-5:
3,3'-diaminodiphenylsulfone ##STR23## Y-6:
1,4-bis(4-aminophenoxy)benzene ##STR24## Y-7:
1,3-bis(3-aminophenoxy)benzene ##STR25## Y-8:
bis[4-(4-aminophenoxy)phenyl]sulfone ##STR26## Y-9:
4,4'-bis(3-aminophenoxy)biphenyl ##STR27## Y-10:
4,4'-diaminodiphenylether ##STR28## Y-11: p-phenylene diamine
##STR29## Y-12: 4,4'-diaminodiphenylsufide ##STR30## Y-13:
4,4'-diaminobenzophenone ##STR31## Y-14:
4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenylsulfone ##STR32## Y-15:
3,4'-diaminodiphenylether ##STR33## Y-16:
4,4'-diaminodiphenylsulfoxide ##STR34## Y-17:
3,3'-dimethyl-4,4'-diaminobiphenyl ##STR35## Y-18:
2,4-diaminomesitylene ##STR36## Y-19: m-phenylene diamine ##STR37##
Y-20: 4,4'-diaminodiphenylsulfone ##STR38## Y-21:
2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane ##STR39## Y-22:
3,5-diamino ethylbenzoate ##STR40## Y-23: 2,4-diaminobenzamide
##STR41## Y-24: 3,5-diaminobenzophenone ##STR42## Y-25:
3,5-diamino(2-methacryloxyethyl)benzoate ##STR43## Y-26:
3,5-diaminobenzonitrile ##STR44## Y-27:
2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane ##STR45## Y-28:
4,4'-diamino-3,3',5,5'-tetramethyldiphenylmethane ##STR46##
Compounds used in the Preparations to form --COR or --COR' groups
(R-raw material) are represented by the following symbols.
E-1: 2-hydroxyethyl methacrylate ##STR47## E-2: 2-isocyanateethyl
methacrylate ##STR48## E-3: 2-diethylamino ethyl methacrylate
##STR49## E-4: glycidyl methacrylate ##STR50## E-5: 2-hydroxyethyl
acrylate ##STR51## E-6: N-(2-hydroxyethyl)methacrylamide ##STR52##
E-7: (2-hydroxypropyl)acrylamide ##STR53## E-8:
2-metacryloxyethyltrimethylammoniumhydroxide ##STR54## E-9: ethyl
alchol
[Preparation 1]
16.1 g of X-1, 10.9 g of X-11, 27.0 g of E-1 and 60 ml of
.gamma.-butyrolactone were put in a 500 ml separable flask. 17.0 g
of pyridine was put in the flask with stirring under ice cooling
and the stirring was continued at room temperature for 16 hrs. The
solution containing 40 ml of .gamma.-butyrolactone and 41.2 g of
dicyclohexylcarbodiimide was added under ice cooling in 30 min.
Further, the suspension containing 70 ml of .gamma.-butyrolactone
and 35.0 g of Y-1 was added in 60 min. under ice cooling and then
stirred under ice cooling for 3 hrs. 5 ml of ethyl alcohol was
added and stirred for 1 hr. Then, the resultant was filtered to
remove solid materials formed in the above process. The filtered
reaction solution was added to 10 l of ethyl alcohol so that
precipitates were formed. The resultant precipitates were separated
from the solution by filtration and dried in vacuum.
Thus, polyimide precursor (A1-1) was prepared. Its viscosity
number, amide bond density and precursor absorbance are shown in
Table 5.
[Preparation 2]
62.0 g of X-2 and 462 ml of N,N'-dimethylacetamide (hereinafter
referred to as DMAc) were put in a 500 ml separable flask. 100 ml
of DMAc and 68.4 g of Y-2 were put in the flask with stirring under
ice cooling and the stirring was continued at room temperature for
16 hrs. Further, 43.4 g of E-2 was added under ice cooling and
stirred for 3 hrs. The resultant reaction solution was added to 10
l of ethyl alcohol so that precipitates were formed. The
precipitates were separated from the solution by filtration and
dried in vacuum.
Thus, polyimide precursor (A2-1) was prepared. Its viscosity
number, amide bond density and precursor absorbance are shown in
Table 5.
[Preparation 3]
76.8 g of Y-3 was dissolved in 450 g of N-methylpyrrolidone. 71.6 g
of X-3 was added to the resultant solution and reacted at
50.degree. C. for 6 hrs. A solution obtained by dissolving 74.0 g
of E-3 in 110 g of N-methylpyrrolidone was slowly added to the
above reacted solution at room temperature. As a result, a solution
of polyimide precursor (A3-1) was obtained. Amide bond density and
precursor absorbance of A3-1 are shown in Table 5.
[Preparation 4]
121.1 g of Y-4 was dissolved in 687 g of N-methyl-pyrrolidone. 88.2
g of X-8 was added to the resultant solution and stirred at room
temperature for 12 hrs. Then, 85.3 g of E-4 was added to the
stirred solution and further stirred at 70.degree. C. for 36 hrs.
As a result, a solution of polyimide precursor (A4-1) was obtained.
Amide bond density and precursor absorbance of A4-1 are shown in
Table 5.
[Preparation 5]
72.9 g of X-4 was dissolved in 200 g of N-methylpyrrolidone. 5.2 g
of E-1 was added to the resultant solution and heated at
100.degree. C. for 1 hr. After that, the solution was cooled to
50.degree. C. 44.4 g of Y-5 and 110 g of N-methylpyrrolidone were
added to the cooled solution and stirred at 50.degree. C. for 5
hrs. Then, 76.0 g of trifluoro acetic anhydride and 280 ml of
tetrahydrofuran were added to the solution and stirred at
50.degree. C. for 2 hrs. While stirring, insoluble solid materials
were separated out. 52.0 g of E-1 was added to the solution
containing the insoluble solid materials and stirred at 50.degree.
C. for 5 hrs. The resultant insoluble solid materials were
dissolved and a uniform solution was obtained. The uniform solution
was poured in 10 l of water to form precipitates. The precipitates
were separated from the solution by a filtration and dried in
vacuum after being washed with water.
Thus, polyimide precursor (A5-1) was prepared. Its viscosity
number, amide bond density and precursor absorbance are shown in
Table 5.
[Preparations 6 to 17]
Polyimide precursors (A1-2 to A1-17) were prepared in the same
manner as in Preparation 1 except that ATC dianhydrides, aromatic
diamino compounds and R-raw materials shown in Table 1 were used
respectively in the amounts shown in Table 1. Their viscosity
numbers, amide bond density and precursor absorbance are shown in
Table 5.
[Preparations 18 to 25]
Solutions of polyimide precursors (A3-2 to A3-9) were prepared in
the same manner as in Preparation 3 except that ATC dianhydrides,
aromatic diamino compounds and R-raw materials shown in Table 2
were used respectively in the amounts shown in Table 2. Their amide
bond density and precursor absorbance are shown in Table 6.
[Preparations 26 to 28]
Polyimide precursors (A5-2 to A5-4) were prepared in the same
manner as in Preparation 5 except that ATC dianhydrides shown in
Table 2 were used in the amounts shown in Table 2. Their viscosity
numbers, amide bond density and precursor absorbance are shown in
Table 6.
[Preparations 29 and 30]
Polyimide precursors (A1-14 and A1-15) were prepared in the same
manner as in Preparation 1 except that ATC dianhydrides, aromatic
diamino compounds and R-raw materials shown in Table 2 were used
respectively in the amounts shown in Table 2. Their viscosity
numbers, amide bond density and precursor absorbance are shown in
Table 6.
[Preparation 31]
31.0 g of X-2, 17.0 g of pyridine and 60 ml of
.gamma.-butyrolactone were put in a 500 ml separable flask. 27.0 g
of E-1 was put in the flask with stirring. After being heated to
40.degree. C. and maintained at that temperature for 4 hrs., the
resultant solution was stirred at room temperature for 16 hrs. The
solution containing 40 ml of 7-butyrolactone and 41.2 g of
dicyclohexylcarbodiimide was added under ice cooling in 30 min.
Further, the suspension containing 80 ml of .gamma.-butyrolactone
and 40.4 g of Y-8 was added in 60 min. and then stirred under ice
cooling for 3 hrs. 5 ml of ethyl alcohol was added and stirred for
1 hr. Then, the resultant solution was filtered to remove solid
materials formed in the above process. The filtered reaction
solution was poured in 10 l of ethyl alcohol so that precipitates
were formed. The precipitates were separated from the solution by
filtration and dried in vacuum.
Thus, polyimide precursor (A1-16) was prepared. Its viscosity
number, amide bond density and precursor absorbance are shown in
Table 5.
[Preparation 32]
Polyimide precursor (A1-17) was prepared in the same manner as in
Preparation 1 except that an ATC dianhydride and an aromatic
diamino compound shown in Table 2 were used respectively in the
amounts shown in Table 2 and the solution containing 160 ml of
1-butyrolactone and 23.6 g of Y-5 was used instead of the
suspension containing 70 ml of .gamma.-butyrolactone and 35.0 g of
Y-1. Its viscosity number, amide bond density and precursor
absorbance are shown in Table 6.
[Preparation 33]
Polyimide precursor (A2-2) was prepared in the same manner as in
Preparation 2 except that an ATC dianhydride, an aromatic diamino
compound and a R-raw material shown in Table 2 are used
respectively in the amounts shown in Table 2. Its viscosity number,
amide bond density and precursor absorbance are shown in Table
6.
[Preparation 34]
160.6 g of Y-7 was dissolved in 770 g of N-methylpyrrolidone. 120 g
of X-11 was added to the resultant solution and reacted at
50.degree. C. for 6 hrs. A solution obtained by dissolving 2.5 g of
E-3 in 50 g of N-methylpyrrolidone was added to 50 g of the above
reacted solution. As a result, a solution of polyimide precursor
(A3-10) was obtained. The amide bond density and precursor
absorbance of A3-10 are shown in Table 6.
[Preparations 35 to 43]
Polyimide precursors (A1-18 to A1-26) were prepared in the same
manner as in Preparation 32 except that ATC dianhydrides, aromatic
diamino compounds and R-raw materials shown in Table 3 were used
respectively in the amounts shown in Table 3. Their viscosity
numbers, amide bond density and precursor absorbance are shown in
Table 7.
[Preparation 44]
22.8 g of Y-20 was dissolved in 150 g of N-methylpyrrolidone. 35.8
g of X-3 was added to the resultant solution and reacted at
50.degree. C. for 6 hrs. A solution obtained by dissolving 37.2 g
of E-3 in 66 g of N-methylpyrrolidone was slowly added to the above
reacted solution at room temperature. As a result, a solution of
polyimide precursor (A3-11) was obtained. Amide bond density and
precursor absorbance of A3-11 are shown in Table 5.
[Preparations 45 to 48]
Polyimide precursors (A1-28 to A1-31) were prepared in the same
manner as in Preparation 32 except that ATC dianhydrides, aromatic
diamino compounds and R-raw materials shown in Table 3 were used
respectively in the amounts shown in Table 3. Their viscosity
numbers, amide bond density and precursor absorbance are shown in
Table 7.
[Preparations 49 and 50]
Solutions of polyimide precursors (A4-2 and A4-3) were prepared in
the same manner as in Preparation 4 except that ATC dianhydrides
and aromatic diamino compounds shown in Table 3 were used
respectively in the amounts shown in Table 3. Viscosity numbers,
amide bond density and precursor absorbance of A4-2 and A4-3 are
shown in Table 7.
[Preparations 51 and 52]
Solutions of polyimide precursors (A3-12 and A3-13) were prepared
in the same manner as in Preparation 44 except that R-raw materials
shown in Table 4 were used respectively in the amounts shown in
Table 4. Viscosity numbers, amide bond density and precursor
absorbance of A3-12 and A3-13 are shown in Table 8.
[Preparations 53 to 58]
Polyimide precursors (A1-32 to A1-37) were prepared in the same
manner as in Preparation 43 except that ATC dianhydrides and
aromatic diamino compounds shown in Table 4 were used respectively
in the amounts shown in Table 4. Their viscosity numbers, amide
bond density and precursor absorbance are shown in Table 8.
[Preparations 59 and 60]
Polyimide precursors (A5-5 and A5-6) were prepared in the same
manner as in Preparation 5 except that ATC dianhydrides shown in
Table 4 were used respectively in the amounts shown in Table 4.
Their viscosity numbers, amide bond density and precursor
absorbance are shown in Table 8.
[Preparation 61]
Polyimide precursor (A1-38) was prepared in the same manner as in
Preparation 32 except that an ATC dianhydride, an aromatic diamino
compound and a R-raw material shown in Table 4 were used
respectively in the amounts shown in Table 4. Its viscosity number,
amide bond density and precursor absorbance are shown in Table
8.
TABLE 1 ______________________________________ Aromatice ATC
dianhydride diamino compound R-raw material Amount Amount Amount
Polyimide Type (g) Type (g) Type (g) precursor
______________________________________ 1 X-1 16.1 Y-1 35.0 E-1 27.0
A1-1 X-11 10.9 2 X-2 62.0 Y-2 68.4 E-2 43.4 A2-1 3 X-3 71.6 Y-3
76.8 E-3 74.0 A3-1 4 X-8 88.2 Y-4 121.1 E-4 85.3 A4-1 5 X-4 72.9
Y-5 44.4 E-1 57.2 A5-1 6 X-1 32.1 Y-6 27.8 E-1 27.0 A1-2 7 Y-7 27.8
A1-3 8 Y-8 40.4 A1-4 9 Y-4 40.4 A1-5 10 Y-9 34.3 A1-6 11 Y-10 18.7
A1-7 12 Y-11 10.3 A1-8 13 Y-14 58.5 A1-9 14 Y-8 40.4 E-5 23.9 A1-10
15 E-1 13.5 A1-11 E-9 4.6 16 E-6 26.8 A1-12 17 E-7 27.0 A1-13
______________________________________
TABLE 2 ______________________________________ Aromatice ATC
dianhydride diamino compound R-raw material Amount Amount Amount
Polyimide Type (g) Type (g) Type (g) precursor
______________________________________ 18 X-3 71.6 Y-5 49.6 E-3
74.0 A3-2 19 Y-12 43.2 A3-3 20 Y-13 42.4 A3-4 21 X-3 71.6 Y-15 40.0
A3-5 22 Y-16 46.4 E-3 74.0 A3-6 23 Y-17 42.4 A3-7 24 Y-5 49.6 E-8
75.6 A3-8 25 E-3 44.4 A3-9 26 X-5 79.2 Y-5 44.4 E-1 57.2 A5-2 27
X-6 94.2 A5-3 28 X-7 106.8 A5-4 29 X-7 54.2 Y-14 58.5 E-1 27.0
A1-14 30 X-3 35.8 Y-8 40.4 A1-15 31 X-2 31.0 Y-8 40.4 A1-16 32 X-1
16.1 Y-5 23.6 A1-17 X-11 10.9 33 X-1 64.4 Y-18 28.0 E-2 31.0 A2-2
34 X-11 120.0 Y-7 160.6 E-3 2.5 A3-10
______________________________________
TABLE 3 ______________________________________ Aromatice ATC
dianhydride diamino compound R-raw material Amount Amount Amount
Polyimide Type (g) Type (g) Type (g) precursor
______________________________________ 35 X-1 32.2 Y-4 20.2 E-1
27.0 A1-18 Y-8 20.2 36 X-11 21.8 Y-4 28.3 A1-19 Y-9 10.3 37 X-1
32.2 Y-4 24.2 A1-20 Y-21 19.4 38 Y-19 10.1 A1-21 39 X-11 21.8 A1-22
Y-4 40.4 40 X-8 29.4 A1-23 41 X-1 32.2 Y-19 6.1 E-1 27.0 A1-24 Y-10
7.5 42 Y-27 48.5 A1-25 43 Y-20 23.6 26.0 A1-26 44 X-3 35.8 Y-20
22.8 E-3 37.2 A3-11 45 X-11 21.8 Y-5 23.6 E-1 26.0 A1-28 46 X-2
31.0 Y-20 23.6 A1-29 47 X-1 32.2 Y-13 21.2 A1-30 48 X-3 35.8 Y-16
22.0 A1-31 49 X-1 32.2 Y-5 23.6 E-4 85.3 A4-2 50 X-2 31.0 A4-3
______________________________________
TABLE 4 ______________________________________ Aromatice ATC
dianhydride diamino compound R-raw material Amount Amount Amount
Polyimide Type (g) Type (g) Type (g) precursor
______________________________________ 51 X-3 35.8 Y-20 22.8 E-8
37.8 A3-12 52 E-3 22.2 A3-13 53 X-1 32.2 Y-22 16.8 E-1 26.0 A1-32
54 X-8 29.4 Y-23 14.0 A1-33 55 X-11 21.8 Y-24 19.7 A1-34 56 X-8
29.4 Y-25 24.6 A1-35 57 X-2 31.0 Y-10 18.5 A1-36 58 X-1 32.2 Y-26
12.4 A1-37 59 X-9 54.8 Y-5 44.4 57.2 A5-5 60 X-10 60.7 A5-6 61 X-1
32.2 Y-28 24.1 E-1 27.0 A1-38
______________________________________
TABLE 5
__________________________________________________________________________
Viscosity Amide *.sup.1 *.sup.1 *.sup.2 Polyimide number bond
density Precursor Condition Condition Condition .sup.3 precursor
(dl/g) (mol/kg) absorbance (i) (ii) (iii) Ex.
__________________________________________________________________________
1 A1-1 0.38 2.32 1.4 .smallcircle. x x 1 2 A2-1 0.48 2.42 1.4
.smallcircle. .smallcircle. x 2 3 A3-1 -- 1.80 0.6 .smallcircle. x
x 3 4 A4-1 -- 1.98 1.2 .smallcircle. x 2, 4 4 5 A5-1 0.92 2.38 0.7
.smallcircle. x 2, 4 5 6 A1-2 0.53 2.39 1.2 .smallcircle. x x 6 7
A1-3 0.25 2.39 1.0 .smallcircle. x 2 7 8 A1-4 0.65 2.04 1.1
.smallcircle. x 3, 4 8 9 A1-5 0.25 2.04 0.57 .smallcircle. x 2, 4 9
10 A1-6 0.32 2.19 0.64 .smallcircle. x 2 10 11 A1-7 0.42 2.68 2.7 x
x x Comp. Ex. 1 12 A1-8 0.39 3.06 6.0 x x x Comp. Ex. 2 13 A1-9
0.53 1.72 0.3 .smallcircle. x 3 11 14 A1-10 0.34 2.11 0.9
.smallcircle. x 3, 4 12 15 A1-11 0.40 2.24 0.9 .smallcircle. x 3, 4
13 16 A1-12 0.31 2.05 0.8 .smallcircle. x 3, 4 14 17 A1-13 0.38
2.04 0.8 .smallcircle. x 3, 4 15
__________________________________________________________________________
*.sup.1 : Condiitons (i) and (ii) conrrespond to conditions (i) and
(ii) in the claims. .smallcircle.: satisfying conditions (i) and
(ii) x: Not satisfying conditions (i) and (ii) *.sup.2 : Condition
(iii) corresponds to conditions (iii1) to (iii4) in the claims.
Numbers: Indicating the numbers of condition (iii) when condition
(iii) is satisfied. x: Not satisfying condition (iii) *.sup.3 : The
number indicates the example where the polyimide precursor is
used.
TABLE 6
__________________________________________________________________________
Viscosity Amide *.sup.1 *.sup.1 *.sup.2 Polyimide number bond
density Precursor Condition Condition Condition .sup.3 precursor
(dl/g) (mol/kg) absorbance (i) (ii) (iii) Ex.
__________________________________________________________________________
18 A3-2 -- 2.05 0.7 .smallcircle. x 2, 4 19 19 A3-3 -- 2.12 1.2
.smallcircle. x x 20 20 A3-4 -- 2.13 1.0 .smallcircle. x 3, 4 21 21
A3-5 -- 2.16 1.0 .smallcircle. x x 22 22 A3-6 -- 2.08 1.4
.smallcircle. x 3, 4 23 23 A3-7 -- 2.13 1.4 .smallcircle. x x 24 24
A3-8 -- 2.11 0.6 .smallcircle. x 2, 4 25 25 A3-9 -- 2.42 0.6
.smallcircle. x 2, 4 26 26 A5-2 0.33 2.29 0.4 .smallcircle.
.smallcircle. 2, 4 16 27 A5-3 0.31 2.11 0.3 .smallcircle.
.smallcircle. 2, 4 17 28 A5-4 0.30 1.97 0.5 .smallcircle.
.smallcircle. 2, 4 18 29 A1-14 0.32 1.45 0.3 x .smallcircle. 3 Comp
Ex. 3 30 A1-15 0.35 1.97 0.6 .smallcircle. x 3, 4 27 31 A1-16 0.34
2.07 0.3 .smallcircle. .smallcircle. 3, 4 28 32 A1-17 0.32 2.70 1.3
x x 2, 4 29 33 A2-2 0.42 3.19 1.3 x x 1 30 34 A3-10 0.28 3.30 1.1 x
x 2 31
__________________________________________________________________________
*.sup.1 : Condiitons (i) and (ii) conrrespond to conditions (i) and
(ii) in the claims. .smallcircle.: satisfying conditions (i) and
(ii) x: Not satisfying conditions (i) and (ii) *.sup.2 : Condition
(iii) corresponds to conditions (iii1) to (iii4) in the claims.
Numbers: Indicating the numbers of condition (iii) when condition
(iii) satisfied. x: Not satisfying condition (iii) *.sup.3 : The
number indicates the example where the polyimide precursor is
used.
TABLE 7
__________________________________________________________________________
Viscosity Amide *.sup.1 *.sup.1 *.sup.2 Polyimide number bond
density Precursor Condition Condition Condition .sup.3 precursor
(dl/g) (mol/kg) absorbance (i) (ii) (iii) Ex.
__________________________________________________________________________
35 A1-18 0.26 2.04 0.95 .smallcircle. x 2, 3, 4 32 36 A1-19 0.28
2.09 1.1 .smallcircle. x 2, 4 33 37 A1-20 0.30 1.99 0.96
.smallcircle. x 2, 4 Comp. Ex. 4 38 A1-21 0.26 3.06 1.4 x x 1 34 39
A1-22 0.28 2.29 0.72 .smallcircle. x 2, 4 35 40 A1-23 0.20 2.11
0.60 .smallcircle. x 2, 4 36 41 A1-24 0.34 2.90 2.0 x x 1 Comp. Ex.
5 42 A1-25 0.28 1.88 0.48 .smallcircle. x x Comp. Ex. 6 43 A1-26
0.30 2.52 1.3 x x 3, 4 37 44 A3-11 0.29 2.04 0.8 .smallcircle. x 3,
4 43 45 A1-28 0.33 2.90 1.2 x x 2, 4 38 46 A1-29 0.25 2.56 1.1 X
.smallcircle. 3, 4 39 47 A1-30 0.31 2.64 1.3 x x 3 40 48 A1-31 0.30
2.57 1.2 x x 3, 4 46 49 A4-2 0.24 2.34 1.3 .smallcircle. x 2, 4 41
50 A4-3 0.25 2.38 1.1 .smallcircle. .smallcircle. 2, 4 42
__________________________________________________________________________
*.sup.1 : Condiitons (i) and (ii) conrrespond to conditions (i) and
(ii) in the claims. .smallcircle.: satisfying conditions (i) and
(ii) x: Not satisfying conditions (i) and (ii) *.sup.2 : Condition
(iii) corresponds to conditions (iii1) to (iii4) in the claims.
Numbers: Indicating the numbers of condition (iii) when condition
(iii) is satisfied. x: Not satisfying condition (iii) *.sup.3 : The
number indicates the example where the polyimide precursor is
used.
TABLE 8
__________________________________________________________________________
Viscosity Amide *.sup.1 *.sup.1 *.sup.2 Polyimide number bond
density Precursor Condition Condition Condition .sup.3 precursor
(dl/g) (mol/kg) absorbance (i) (ii) (iii) Ex.
__________________________________________________________________________
51 A3-12 0.31 2.03 0.8 0 x 3, 4 44 52 A3-13 0.36 2.42 0.9 0 x 3, 4
45 53 A1-32 0.46 2.75 0.5 x x 4 47 54 A1-33 0.22 2.87 1.2 x x 4 48
55 A1-34 0.39 3.06 0.8 x x 4 49 56 A1-35 0.26 2.56 0.4 x x 4 50 57
A1-36 0.49 2.72 0.6 x .smallcircle. x 51 58 A1-37 0.48 2.95 0.9 x x
4 52 59 A5-5 0.39 2.67 0.3 x .smallcircle. 2, 4 53 60 A5-6 0.38
2.56 0.8 x .smallcircle. 2, 4 54 61 A1-38 0.35 2.5 1.8 x x x Comp.
Ex. 7
__________________________________________________________________________
*.sup.1 : Condiitons (i) and (ii) conrrespond to conditions (i) and
(ii) in the claims. .smallcircle.: Satisfying conditions (i) and
(ii) x: Not satisfying conditions (i) and (ii) *.sup.2 : Condition
(iii) corresponds to conditions (iii1) to (iii4) in the claims.
Numbers: Indicating the numbers of condition (iii) when condition
(iii) is satisfied. x: Not satisfying condition (iii) *.sup.3 : The
number indicates the example where the polyimide precursor is
used.
Before describing the Examples, symbols used for each compound in
the Examples are shown.
Photopolymerization initiator (Component (B))
I-1: benzophenone
I-2: benzyl
I-3: 2-isopropylthioxanthone
I-4: 1,3-diphenyl-propanetrione-2-(O-ethoxycarbonyl)oxime
I-5: 1-phenyl-3-ethoxy-propanetrione-2-(O-benzoyl)oxime
Reactive carbon--carbon double bond-containing compound
M-1: tetraethylene glycol dimethacrylate
M-2: pentaerythritol diacrylate
M-3: methylenebisacrylamide
M-4: N-methylolacrylamide
M-5: trimethylolpropane triacrylate
Sensitizer
S-1: Michler's ketone
S-2: 4,4'-bis(diethylamino)benzophenone
S-3: 2-(p-dimethylaminostyryl)benzoxazole
S-4: 2-(p-dimethylaminobenzoyl)styrene
S-5: N-phenyldiethanolamine
S-6: N-p-toluyldiethanolamine
S-7: N-phenylethanolamine
S-8: 2-mercaptobenzimidazole
S-9: 1-phenyl-5-mercapto-1,2,3,4-tetrazole
S-10: 2-mercaptobenzothiazole
Adhesion promoter
F-1: .gamma.-glycidoxypropylmethyldimethoxysilane
F-2: 3-methacryloxypropyltrimethoxysilane
F-3: 3-methacryloxypropylmethyldimethoxysilane
F-4: N-[3-(triethoxysilyl)propyl]phthalamic acid
F-5:
benzophenone-3,3'-bis(3-triethoxysilylpropylaminocarbonyl)-4,4'-dicarboxyl
ic acid
Polymerization inhibitor
Z-1: N-nitrosodiphenylamine
Z-2: bis(4-hydroxy-3,5-tert-butylphenyl)methane
Z-3: 2,6-di-tert-butyl-p-methylphenol
Z-4: 2-nitroso-l-naphthol
EXAMPLE 1
50 g of polyimide precursor (A1-1), 2 g of I-1, 6 g of M-1, 0.05 g
of S-1, 1 g of S-5, 1.5 g of S-8, 1 g of F-i and 0.05 g of Z-1 were
dissolved in 75 g of N-methylpyrrolidone to obtain photosensitive
composition (W-1). Its coating absorbance and viscosity were 1.5
and 73.5 P, respectively.
The obtained composition was applied on 3 inch silicon wafers by
using a spin-coater, and dried to form 13 mm thick films. Using an
i-line stepper FPA 2001 iI (manufactured by Canon Inc.), the films
on the wafers were exposed through a patterned reticle at an
exposure energy of 800 mJ/cm.sup.2. Then, they were developed by
spraying a mixed solvent of .gamma.-butyrolactone and xylene (50/50
vol. %) and rinsed with isopropyl alcohol. As a result, a sharp 10
.mu.m line/space pattern was obtained.
The irradiated films on the wafers were heat-cured at 140.degree.
C. for 1 hr. and at 300.degree. C. for 1 hr. under nitrogen
atmosphere in a convection oven to obtain 7 mm thick patterned
polyimide films. The resultant films were broken at a pulling
stress of 8 kg/cm.sup.2 in both of the pull and water resistance
tests. They showed good adhesive strength and water resistance. The
tensile strength and elongation of the polyimide films were 14
kg/mm.sup.2 and 30%, respectively.
EXAMPLE 2
20 g of polyimide precursor (A-2), 0.3 g of I-2, 0.5 g of M-2, 0.02
g of S-2, 0.1 g of S-9, 0.15 g of F-3 and 0.01 g of Z-2 were
dissolved in 40 g of N-methylpyrrolidone to obtain photosensitive
composition (W-2). Its coating absorbance and viscosity were 1.5
and 44 P, respectively.
The obtained composition was applied on 3 inch silicon wafers by
using a spin-coater, and dried to form 13 .mu.m thick films. Using
an i-line stepper NSR-1505 i7A (manufactured by Nikon Corporation),
the films on the wafers were exposed through a patterned reticle at
an exposure energy of 400 mJ/cm.sup.2. Then, they were developed in
a mixed solvent of tetramethyl ammonium hydroxide, methyl alcohol
and water (0.3/2.7/97 vol. %), and rinsed with water. As a result a
sharp 10 .mu.m line/space pattern was obtained.
The irradiated films on the wafers were baked at 200.degree. C. for
10 min. on a hot plate and heat-cured at 350.degree. C. for 1 hr.
under nitrogen atmosphere in a curing furnace to form 7 .mu.m thick
polyimide patterned films. The resultant films were broken at a
pulling stress of 8 kg/mm.sup.2 in both of the pull and water
resistance tests. They showed good adhesive strength and water
resistance. The tensile strength and elongation of the polyimide
films were 20 kg/mm.sup.2 and 9%, respectively.
EXAMPLE 3
0.2 g of I-3, 0.8 g of M-3, 0.02 g of S-3, 0.3 g of S-6, 0.15 g of
S-10, 0.1 g of F-3 and 0.01 g of Z-3 were dissolved in 77 g of the
solution of polyimide precursor (A3-1) prepared in Preparation 3 to
obtain photosensitive composition (W-3). Its coating absorbance and
viscosity were 0.8 and 55.0 P, respectively.
The obtained composition was applied on 3 inch silicon wafers by
using a spin-coater, and dried to form 17 mm thick films. Using an
exposure machine PLA 501F (manufactured by Canon Inc.) and i-line
band pass filter UVD 36C (manufactured by Toshiba Glass Co., Ltd.),
the films on the wafers were exposed through a photomask at an
exposure energy of 1000 mJ/cm.sup.2. Then, they were developed by
spraying a mixed solvent of N,N'-dimethylacetoamide and ethyl
alcohol (80/20 vol. %), and rinsed with isopropyl alcohol. As a
result, a sharp 10 .mu.m line/space pattern was obtained.
The irradiated films on the wafers were heat-cured at 140.degree.
C. for 1 hr. and at 300.degree. C. for 1 hr. under nitrogen
atmosphere in a convection oven to form 8 mm thick patterned
polyimide films. The resultant films were broken at a pulling
stress of 8 kg/mm.sup.2 in both of the pull and water resistance
tests. They showed good adhesive strength and water resistance. The
tensile strength and elongation of the polyimide films were 12
kg/mm.sup.2 and 70%, respectively.
EXAMPLE 4
0.6 g of I-4, 0.8 g of M-4, 0.03 g of S-4, 0.2 g of S-7, 0.1 g of
S-8, 0.1 g of F-4 and 0.01 g of Z-4 were dissolved in 33.3 g of the
solution of polyimide precursor (A4-1) prepared in Preparation 4 to
obtain photosensitive composition (W-4). Its coating absorbance and
viscosity were 1.5 and 38 P, respectively.
The obtained composition was applied on 3 inch silicon wafers by
using a spin-coater, and dried to form 13 .mu.m thick films. Using
an i-line stepper FPA 2001 iI (manufactured by Canon Inc.), the
films on the wafers were exposed through a patterned reticle at an
exposure energy of 800 mJ/cm.sup.2. Then, they were developed in a
mixed solvent of cholinhydroxide, ethyl alcohol and water
(0.5/0.5/90 vol. %) by means of puddle development. As a result, a
sharp 10 .mu.m line/space pattern was obtained.
The irradiated films on the wafers were heat-cured at 140.degree.
C. for 1 hr. and at 300.degree. C. for 1 hr. under nitrogen
atmosphere in a convection oven to form 7 mm thick polyimide films.
The resultant films were broken at a pulling stress of 8
kg/mm.sup.2 in both of the pull and water resistance test. They
showed good adhesive strength and water resistance. The tensile
strength and elongation of the polyimide films were 18 kg/mm.sup.2
and 12%, respectively.
EXAMPLE 5
50 g of polyimide precursor (A5-1), 2 g of I-5, 3 g of M-5, 0.1 g
of S-3, 0.5 g of S-9, 1 g of F-5 and 0.02 g of Z-4 were dissolved
in 75 g of N-methylpyrrolidone to obtain photosensitive composition
(W-5). Its coating absorbance and viscosity were 1.0 and 47.0 P,
respectively.
The obtained composition was applied on 3 inch thick silicon wafers
by using a spin-coater, and dried to form 19 .mu.m thick films.
Using an i-line stepper FPA 2001 iI (manufactured by Canon Inc.),
the films on the wafers were exposed through a patterned reticle at
an exposure energy of 600 mJ/cm.sup.2. Then, they were developed in
a mixed solvent of cyclohexanone and xylene (70/30 vol. %), and
rinsed with isopropyl alcohol. As a result a sharp 15 mm line/space
pattern was obtained.
The irradiated films on the wafers were heat-cured at 140.degree.
C. for 1 hr. and at 350.degree. C. for 2 hrs. under nitrogen
atmosphere in a convection oven to obtain a 10 .mu.m patterned
polyimide films. The resultant films were broken at a pulling
stress of 8 kg/mm.sup.2 in both of the pull and water resistance
tests. They showed good adhesive strength and water resistance. The
tensile strength and elongation of the polyimide films were 18
kg/mm.sup.2 and 18%, respectively.
EXAMPLES 6 to 18
50 g of various kinds of polyimide precursors shown in Table 9, 2 g
of I-5, 3 g of M-5, 0.3 g of S-3, 0.5 g of S-9, 1 g of F-5 and 0.02
g of Z-4 were dissolved in 75 g of N-methylpyrrolidone to obtain
photosensitive compositions (W-6 to W-18). Their coating absorbance
and viscosity are shown in Table 9.
The obtained compositions were applied on 3 inch thick silicon
wafers by using a spin-coater, and dried. The thickness of the
resultant films is shown in Table 9. Using an i-line stepper FPA
2001 iI (manufactured by Canon Inc.), the films on the wafers were
exposed through a patterned reticle at an exposure energy of 800
mJ/cm.sup.2. Then, they were developed in a mixed solvent of
cyclohexane and xylene (70/30 vol. %), and rinsed with isopropyl
alcohol. The resultant resolution of the films is shown in Table
9.
The irradiated films on the wafers were heat-cured at 140.degree.
C. for 1 hr. and at 350.degree. C. for 2 hrs. under nitrogen
atmosphere in a convection oven to obtain polyimide patterned films
having thickness shown in Table 9. The results of the pull and
water resistance tests and the tensile strength and elongation of
the polyimide films are shown in Table 9.
EXAMPLES 19 to 26
Photosensitive compositions (W-19 to W-26) were prepared by the
same method as in Example 3 except that various kinds of polyimide
precursor solutions, which are shown in Table 10, prepared in
Preparations 18 to 25 were employed instead of the polyimide
precursor (A3-1). Their coating absorbance and viscosity are shown
in Table 10.
Using these compositions, films were produced by the same method as
in Example 3 and subjected to the same tests as in Example 3. The
resolution of the patterned films, the results of the pull and
water resistance tests, and the tensile strength and elongation of
the polyimide films are shown in Table 10.
EXAMPLES 27 and 28
50 g of a polyimide precursor shown in Table 10, 2 g of I-5, 3 g of
M-5, 0.1 g of S-3, 0.5 g of S-9, 1 g of F-5 and 0.02 g of Z-4 were
dissolved in 75 g of N-methylpyrrolidone to obtain photosensitive
compositions (W-27 and W-28). Their coating absorbance and
viscosity are shown in Table 10.
Using these compositions, films were produced by the same method as
in Example 1 and subjected to the same tests as in Example 1. The
resolution of the patterned films, the results of the pull and
water resistance test, and the tensile strength and elongation of
the polyimide films are shown in Table 10.
COMPARATIVE EXAMPLES 1 and 2
50 g of a polyimide precursor shown in Table 10, 2 g of I-5, 3 g of
M-5, 0.05 g of S-3, 0.5 g of S-9, 1 g of F-5 and 0.02 g of z-4 were
dissolved in 75 g of N-methylpyrrolidone to obtain photosensitive
compositions (WR-1 and WR-2). Their coating absorbance and
viscosity are shown in Table 10.
Using these compositions, films were produced by the same method as
in Example 6. The resultant films in Comparative Example 1 did not
have clear line because a cross-section of the line showed an
inverse trapezoid having a sharp inclination so that they were not
applicable to practical uses, neither were the resultant films in
Comparative Example 2 because of an extremely sharp inclination.
The results of the pull and water resistant tests, and the tensile
strength, elongation and thickness of the polyimide films are shown
in Table 10.
COMPARATIVE EXAMPLE 3
The general procedure of Comparative Example 1 was repeated except
that polyimide precursor (A1-14) was used instead of polyimide
precursor (A1-7) to prepare photosensitive composition (WR-3). Its
coating absorbance and viscosity were 0.41 and 66.3 P,
respectively.
The obtained composition was applied on 3 inch silicon wafers by
using a spin-coater and dried to form 27 mm thick films. The
resultant films produced by the same method as in Example 1 did not
show line/space because irradiated areas were extremely swelled. On
the other hand, the resultant films were broken at a pulling stress
of 8 kg/mm.sup.2 in both of the pull and water resistance tests.
They showed good adhesive strength and water resistance. The
tensile strength and elongation of the polyimide films were 9
kg/mm.sup.2 and 120%, respectively.
EXAMPLE 29
50 g of polyimide precursor (A1-17), 2 g of I-1, 6 g of M-1, 0.05 g
of S-1, 1 g of S-5, 1.5 g of S-10, 1 g of F-1 and 0.05 g of Z-1
were dissolved in 75 g of N-methylpyrrolidone to obtain
photosensitive composition (W-29). Its coating absorbance and
viscosity were 1.5 and 78 P, respectively.
Using the composition, 13 .mu.m thick films were produced by the
same method as in Example 1. Then, they were developed and rinsed
with xylene to obtain a sharp 10 .mu.m line/space pattern.
The irradiated films on the wafers were heat-cured under the same
condition as in Example 1 to obtain 7 .mu.m thick patterned
polyimide films. The resultant films were broken at a pulling
stress of 8 kg/mm.sup.2 in both of the pull and water resistance
test. They showed good adhesive strength and water resistance. The
tensile strength and elongation of the polyimide films were 15
kg/mm.sup.2 and 14%, respectively.
EXAMPLE 30
0.3 g of I-2, 0.5 g of M-2, 0.02 g of S-2, 0.1 g of S-9, 0.15 g of
F-2 and 0.01 g of Z-2 were dissolved in 55.6 g of polyimide
precursor (A2-2) to obtain photosensitive composition (W-30). Its
coating absorbance and viscosity were 1.5 and 69 P,
respectively.
Using the composition, 13 mm thick films were produced by the same
method as in Example 2. Then, they were developed to obtain a sharp
10 mm line/space pattern.
The irradiated films on the wafers were heat-cured under the same
condition as in Example 2 to obtain 7 mm thick patterned polyimide
films. The resultant films were broken at a pulling stress of 5 to
6 kg/mm.sup.2 in the pull test and at 3 kg/mm.sup.2 or less in the
water resistance test. The tensile strength and elongation of the
polyimide films were 17 kg/mm.sup.2 and 10%, respectively.
EXAMPLE 31
The general procedure in Example 3 was repeated except that
polyimide precursor (A3-10) was used instead of polyimide precursor
(A3-1) to prepare photosensitive composition (W-31). Its coating
absorbance and viscosity was 1.4 and 50 P, respectively.
Using the composition, 17 .mu.m thick films were produced by the
same method as in Example 3. Then, they were developed to obtain a
sharp 10 mm line/space pattern.
The irradiated films on the wafers were heat-cured under the same
condition as in Example 3 to obtain 9 mm thick patterned polyimide
films. The resultant films were broken at a pulling stress of 8
kg/mm.sup.2 in both of the pull and water resistance test. They
showed good adhesive strength and water resistance. The tensile
strength and elongation of the polyimide films were 16 kg/mm.sup.2
and 10%, respectively.
EXAMPLES 32 to 36 and COMPARATIVE EXAMPLES 4 to 6
Various kinds of polyimide precursors and other components shown in
Table 11 were dissolved in 75 g of N-methylpyrrolidone to obtain
photosensitive compositions (W-32 to W-36 and WR-4 to WR-6). Their
coating absorbance and viscosity are shown in Table 12.
The obtained compositions were applied on 3 inch silicon wafers by
using a spin-coater and dried. Thicknesses of the resultant films
are shown in Table 12. Using an i-line stepper FPA 2001 iI
(manufactured by Canon Inc.), the films on the wafers were exposed
through a patterned reticle at an exposure energy shown in Table
11. Then, they were developed in a mixed solvent of cyclohexanone
and xylene (70/30 vol. %) and rinsed with solvents shown in Table
11. The resultant films in the Examples showed sharp patterns.
Their resolution is shown in Table 12.
The irradiated films on the wafers were heat-cured at 140.degree.
C. for 1 hr. and at 350.degree. C. for 2 hrs. under nitrogen
atmosphere in a convection oven. Thickness of the obtained
polyimide films are shown in Table 12. The results of the pull and
water resistance tests, and the tensile strength and elongation of
the polyimide films are shown in Table 12.
EXAMPLES 37 to 40
50 g of various kinds of a polyimide precursor shown in Table 13, 2
g of I-1, 6 g of M-1, 0.05 g of S-1, 1 g of S-5, 1.5 g of S-8, 1 g
of F-1 and 0.05 g of Z-1 were dissolved in 75 g N-methylpyrrolidone
to obtain photosensitive compositions (W-37 to W-40). Their coating
absorbance and viscosity are shown in Table 13.
The obtained compositions were applied on 3 inch silicon wafers by
using a spin-coater and dried. Thickness of the resultant films are
shown in Table 13. Using an i-line stepper and exposure energy
shown in Table 13, the films on the wafers were exposed through a
patterned reticle. Then, they were developed by spraying a mixed
solvent of .gamma.-butyrolactone and xylene (50/50 vol. %) and
rinsed with xylene. The resultant films showed sharp pattern
profiles. Their resolution is shown in Table 13.
The irradiated films on the wafers were heat-cured at 140.degree.
C. for 1 hr. and at 300.degree. C. for 1 hr. under nitrogen
atmosphere in a convection oven to obtain polyimide patterned films
having thickness shown in Table 13. The results of the pull and
water resistance tests, and the tensile strength, elongation and
thickness of the polyimide films are shown in Table 13.
EXAMPLES 41 and 42
0.6 g of I-4, 0.8 g of M-4, 0.03 g of S-4, 0.2 g of S-7, 0.1 g of
S-8, 0.1 g of F-4 and 0.01 g of Z-4 were dissolved in 33.3 g of
polyimide precursor shown in Table 13 to obtain photosensitive
compositions (W-41 and W-42). Their coating absorbance and
viscosity are shown in Table 13.
Using these compositions, films were produced by the same method as
in Example 4 except that an exposure energy of 500 mJ/cm.sup.2 was
employed. Both resultant films showed sharp pattern profiles.
The irradiated films of the wafers were heat-cured at 140.degree.
C. for 1 hr. and at 350.degree. C. for 1 hr. under nitrogen
atmosphere in a convection oven to obtain polyimide patterned films
having a thickness shown in Table 13. The results of the pull and
water resistance tests, and the tensile strength and elongation of
the polyimide films are shown in Table 13.
EXAMPLES 43 to 45
0.2 g of I-3, 0.8 g of M-3, 0.02 g of S-3, 0.3 g of S-6, 0.15 g of
S-10, 0.1 g of F-3 and 0.01 g of Z-3 were dissolved in 77 g of
polyimide precursor shown in Table 13 to obtain photosensitive
compositions (W-43 to W-45). Their coating absorbance and viscosity
are shown in Table 13.
The obtained compositions were applied on 3 inch silicon wafers by
using a spin-coater and dried. Thickness of the resultant films is
shown in Table 13. Using an i-line stepper, the films on the wafers
were exposed through a patterned reticle at exposure energy shown
in Table 13. Then, they were developed by spraying a mixed solvent
of N,N'-dimethylacetamide and ethyl alcohol (80/20 vol. %) and
rinsed with isopropyl alcohol. The resultant films showed sharp
pattern profiles. Their resolution is shown in Table 13.
The irradiated films on the wafers were heat-cured at 140.degree.
C. for 1 hr. and at 350.degree. C. for 1 hr. under nitrogen
atmosphere in a convection oven to obtain polyimide patterned films
having thickness shown in Table 13. The results of the pull and
water resistance tests, and the tensile strength and elongation of
the polyimide films are shown in Table 13.
EXAMPLE 46
50 g of polyimide precursor (A1-31), 2 g of I-1, 6 g of M-1, 0.05 g
of S-1, 1 g of S-5, 1.5 g of S-10, 1 g of F-1 and 0.05 g of Z-1
were dissolved in 75 g of N-methylpyrrolidone to obtain
photosensitive composition (W-46). Its coating absorbance and
viscosity were 1.5 and 43 P, respectively.
The obtained composition was applied on 3 inch silicon wafers by
using a spin-coater and dried to form 13 mm thick films. Using an
i-line stepper NSR-1505 i7A (manufactured by Nikon Corporation),
the films on the wafers were exposed through a patterned reticle at
an exposure energy of 600 mJ/cm.sup.2. Then, they were developed in
a mixed solvent of .gamma.-butyrolactone and xylene (50/50 vol. %)
and rinsed with xylene. As a result, a sharp 10 .mu.m line/space
pattern was obtained.
The irradiated films on the wafers were heat-cured at 140.degree.
C. for 1 hr. and at 300.degree. C. for 1 hr. under nitrogen
atmosphere in a convection oven to obtain 7 .mu.m thick patterned
polyimide films. The resultant films were broken at a pulling
stress of 8 kg/mm.sup.2 in both of the pull and water resistance
tests. They showed good adhesive strength and water resistance. The
tensile strength and elongation of the polyimide films were 14
kg/cm.sup.2 and 15%, respectively.
EXAMPLES 47 and 48
50 g of polyimide precursor shown in Table 14, 2 g of I-5, 3 g of
M-5, 0.1 g of S-3, 0.5 g of S-9, 1 g of F-5 and 0.02 g of Z-4 were
dissolved in N-methylpyrrolidone to obtain photosensitive
compositions (W-47 and W-48). Their coating absorbance and
viscosity are shown in Table 14.
The obtained compositions were applied on 3 inch silicon wafers by
using a spin-coater and dried. Thickness of the resultant films are
shown in Table 14. Using an i-line stepper NSR-1505 i7A
(manufactured by Nikon Corporation), the films on the wafers were
exposed through a patterned reticle at an exposure energy of 500
mJ/cm.sup.2 for W-47 and 600 mJ/cm.sup.2 for W-48 with a mixed
solvent of cyclohexanone and xylene (70/30 vol. %) by means of
puddle development and rinsed with isopropyl alcohol. Both
resultant films showed sharp pattern profiles. The resolution was
shown in Table 14.
The irradiated films on the wafers were heat-cured at 140.degree.
C. for 1 hr. and at 350.degree. C. for 1 hr. under nitrogen
atmosphere in a convection oven to obtain polyimide patterned films
having thickness shown in Table 14. The results of the pull and
water resistance tests, and the tensile strength and elongation of
polyimide films are shown in Table 14.
EXAMPLE 49
General procedure of Example 46 was repeated except that polyimide
precursor (A1-34) was used instead of polyimide precursor (A1-31)
to prepare photosensitive composition (W-49). Its coating
absorbance and viscosity were 1.0 and 44 P, respectively.
Using this composition, 20 .mu.m thick films were produced by the
same method as in Example 46 except that an exposure energy of 200
mJ/mm.sup.2 was used. Then, they were developed to obtain a sharp
15 .mu.m line/space pattern.
The irradiated films on the wafers were heat-cured under the same
condition as in Example 46. The resultant films were broken at a
pulling stress of 8 kg/mm.sup.2 in both of the pull and water
resistance tests. They showed good adhesive strength and water
resistance. The tensile strength and elongation of the polyimide
films were 14 kg/mm.sup.2 and 30%, respectively.
EXAMPLES 50 and 51
50 g of polyimide precursor shown in Table 14, 2 g of I-5, 3 g of
M-5, 0.1 g of S-3, 0.5 g of S-9, 1 g of F-5 and 0.02 g of Z-4 were
dissolved in N-methylpyrrolidone to obtain photosenstive
compositions (W-50 and W-51). Their coating absorbance and
viscosity are shown in Table 14.
Using these compositions, films were produced by the same method as
in Example 5 except for using an exposure energy of 200 mJ/cm.sup.2
for W-50 and 500 mJ/cm.sup.2 for W-51 to obtain sharp patterns.
Their resolution is shown in Table 14.
The irradiated films on the wafers were heat-cured at 140.degree.
C. for 1 hr. and at 350.degree. C. for 1 hr. under nitrogen
atmosphere in a convection oven to obtain polyimide patterned films
having thicknesses shown in Table 14. The results of the pull and
water resistance tests, and the tensile strength and elongation of
the polyimide films are shown in Table 14.
EXAMPLE 52
General procedure of Example 46 was repeated except that polyimide
precursor (A1-37) was used instead of polyimide precursor (A1-31)
and 80 g of N-methylpyrrolidone to prepare photosensitive
composition (W-52). Its coating absorbance and viscosity were 1.2
and 30 P, respectively.
Using this composition, 13 .mu.m thick films were produced by the
same method as in Example 46. Then, they were developed to obtain a
sharp 10 .mu.m line/space pattern.
The irradiated films on the wafers were heat-cured under the same
condition as in Example 46 to obtain 7 .mu.m patterned polyimide
films. The resultant films were broken at a pulling stress of 8
kg/mm.sup.2 in both of the pull and water resistance tests. They
showed good adhesion property and water resistance. The tensile
strength and elongation of the polyimide films were 14 kg/mm.sup.2
and 25%, respectively.
EXAMPLES 53 and 54
General procedure of Example 6 was repeated except that various
polyimide precursors shown in Table 15 were used to prepare
photosensitive compositions (W-53 and W-54). Their coating
absorbance and viscosity are shown in Table 15.
Using these compositions, films were prepared by the same method as
in Example 6. The resolution of the obtained films, the results of
the pull and water resistance tests, and the tensile strength and
elongation are shown in Table 15.
COMPARATIVE EXAMPLE 7
General procedure of Example 6 was repeated except that polyimide
precursor (A1-38) was used instead of polyimide precursor (A1-8) to
prepare photosensitive composition (WR-7). Its coating absorbance
and viscosity were 2.0 and 60.2 P, respectively.
Using the composition, 12 .mu.m thick films were produced by the
same method as in Example 6. After development, the films did not
show clear line/space patterns because a cross-section of the line
showed an inverse trapezoid having a sharp inclination. They were
not workable.
The irradiated films were heat-cured by the same condition as in
Example 6 to obtain 7 mm patterned polyimide films. The resultant
films were broken at 5 kg/mm.sup.2 in the pull test and at 3
kg/mm.sup.2 or less in the water resistance test. The tensile
strength and elongation of the polyimide films were 14 kg/mm.sup.2
and 30%, respectively.
Tests for other physical properties
Other physical properties of photosensitive compositions and
polyimide films obtained therefrom were measured by the following
methods. The results of these tests are shown in Tables 16-18.
(1) Preservation stability test
Photosensitive compositions(W-1 to W-54 and WR-1 to WR-7) prepared,
respectively, in Examples 1 to 54 and Comparative Examples 1 to 7
were preserved in an oven at 40.degree. C. for 5 days. Then,
viscosity and patterning capacity of these compositions were
measured and compared before and after preservation.
(Evaluation)
______________________________________ Change in viscosity
Patterning capacity ______________________________________
.smallcircle. (good) less than .+-.5% Possible to apply and pattern
under the same condition as before preservation. .DELTA. (usable)
.+-.5 to .+-.25% Possible to apply and pattern when spin-coating
conditions are adjusted. x (poor) more than .+-.25% Impossible to
apply and pattern. ______________________________________
(2) Stability in long development
Photosensitive compositions (W-1 to W-54, WR-1 and WR-6) prepared,
respectively, in Examples 1 to 54, Comparative Examples 1 and 6
were applied and exposed. Then, they were developed for a 30%
longer period than each Example or Comparative Example and rinsed
to obtain patterned films.
(Evaluation)
o (good) Sharp patterns were obtained.
.DELTA. (usable) Patterns were slightly swelled.
x (poor) Exposed areas were partly swelled and dissolved, and did
not have resolution.
(3) Heat resistance test of polyimide films.
The polyimide films obtained from Examples 1 to 28 and Comparative
Example 3 were (i) held in a solder bath at 280.degree. C. for 20
sec., (ii) pressed with a metal lever heated at 300.degree. C. for
2 sec. for observation.
(Evaluation)
(i) o (good) No change was observed.
.DELTA. (usable) Shrunk and slightly swelled.
x (poor) Dissolved and impossible to recover.
(ii) o (good) No big change was observed.
.DELTA. (usable) A mark of the lever was observed.
x (poor) A hole was observed.
(4) Elongation of the polyimide films
The polyimide films obtained from Examples 8, 27, 28, 30 and 54 and
Comparative Examples 1, 2 and 7 were held in boiling water for 48
hrs. and dried in an oven at 50.degree. C. for 2 hrs. Then,
elongation of these films were measured and compared before and
after boiling. Before boiling, the elongation of the films obtained
from Examples 8, 27 and 30 were 90%, 27% and 65%, respectively;
after boiling those were 85%, 30% and 65%, respectively. Little
change was observed. On the other hand, the elongation of the films
obtained from Examples 30 and 54 were lowered from 10% and 30% to
5% or less and 15% or less, respectively. Those of Comparative
Examples 1 and 7 were lowered from 30% to 22% and 10%,
respectively. The elongation of the films obtained from Comparative
Example 2 was lowered from 8% to 2% or less.
TABLE 9
__________________________________________________________________________
Polyimide film Water Photosensitive composition Tensile Line/space
Pull resistance Polyimide Coating Viscosity Thickness strength
Elongation Thickness resolution test test Ex. precursor absorbance
(poise) (.mu.m) (kg/mm.sup.2) (%) (.mu.m) (.mu.m) (kg/mm.sup.2)
(kg/mm.sup.2)
__________________________________________________________________________
6 W- 6 A1- 2 1.42 135.0 16 18 59 8 15 8 8 7 W- 7 A1- 3 0.98 48.2 20
12 80 10 20 8 8 8 W- 8 A1- 4 1.35 125.2 18 13 90 10 15 8 8 9 W- 9
A1- 5 0.82 52.8 24 15 12 13 20 8 8 10 W-10 A1- 6 0.89 63.0 23 18 12
13 20 8 8 11 W-11 A1- 9 0.60 77.5 30 11 120 16 20 8 8 12 W-12 A1-10
0.89 69.3 23 13 20 12 20 8 8 13 W-13 A1-11 0.93 72.2 21 13 35 10 15
8 8 14 W-14 A1-12 0.83 48.3 22 12 35 12 20 8 8 15 W-15 A1-13 0.80
49.0 21 13 15 10 20 8 8 16 W-16 A5- 2 1.03 52.2 22 18 22 11 20 8 8
17 W-17 A5- 3 0.98 48.5 20 17 25 10 20 8 8 18 W-18 A5- 4 0.89 49.5
22 15 28 11 20 8 8
__________________________________________________________________________
TABLE 10
__________________________________________________________________________
Polyimide film Water Photosensitive composition Tensile Line/space
Pull resistance Polyimide Coating Viscosity Thickness strength
Elongation Thickness resolution test test Ex. precursor absorbance
(poise) (.mu.m) (kg/mm.sup.2) (%) (.mu.m) (.mu.m) (kg/mm.sup.2)
(kg/mm.sup.2)
__________________________________________________________________________
19 W-19 A3- 2 0.70 73.3 25 18 13 12 15 8 8 20 W-20 A3- 3 1.30 68.3
18 15 35 8 15 8 8 21 W-21 A3- 4 1.29 79.0 18 13 28 9 15 8 8 22 W-22
A3- 5 1.12 53.2 20 16 20 9 15 8 8 23 W-23 A3- 6 1.45 49.8 16 13 20
8 15 8 8 24 W-24 A3- 7 1.42 55.3 16 19 10 7 15 8 8 25 W-25 A3- 8
0.82 59.0 22 15 14 10 20 8 8 26 W-26 A3- 9 0.88 89.8 22 14 15 11 20
8 8 27 W-27 A1-15 0.89 85.3 21 12 28 11 15 8 8 28 W-28 A1-16 0.84
81.3 23 12 65 13 15 8 8 Comp. WR-1 A1- 7 2.52 103.0 12 14 30 6 N.D.
8 4 Ex. 1 Comp. WR-2 A1- 8 6.10 98.0 12 10 8 6 N.D. 8 N.D. Ex. 2
__________________________________________________________________________
N.D.: Not determined
TABLE 11
__________________________________________________________________________
Component of photosensitiv composition Polymeriza- Exposure
Polyimide Photopolymer- C.dbd.C-containing Adhesion tion energy Ex.
precursor ization initiator compound Sensitizer promoter inhibitor
(mJ/cm.sup.2) Rinse
__________________________________________________________________________
32 W-32 A1-18 I-5 2 g M-5 3 g S-3 0.1 g F-5 1 g Z-4 0.02 g 600
Isopropyl S-9 0.5 g alcohol 33 W-33 A1-19 50 g " " " " " 800 " S-3
0.05 g 34 W-34 A1-21 50 g " " S-9 0.5 g " " 400 Xylene S-3 0.1 g
1000 Isopropyl 35 W-35 A1-22 50 g " " S-9 0.5 g " " alcohol 36 W-36
A1-23 50 g " " " " " 1200 Isopropyl alcohol Comp. WR-4 A1-20 50 g "
" " " " 500 Isopropyl Ex. 4 alcohol Comp. WR-5 A1-24 50 g " " S-3
0.05 g " " 400 Xylene Ex. 5 S-9 0.5 g Comp. WR-6 A1-25 50 g " " S-3
0.1 g " " 700 Isopropyl Ex. 6 S-9 0.5 g alcohol
__________________________________________________________________________
TABLE 12
__________________________________________________________________________
Photosensitive composition Polyimide film Water Tensile Pull
resistance Coating Viscosity Thickness Strength Elongation
Thickness test test Ex. absorbance (poise) (.mu.m) (kg/mm.sup.2)
(%) (.mu.m) Line/space resolution (.mu.m) (kg/mm.sup.2)
(kg/mm.sup.2)
__________________________________________________________________________
32 1.1 43 18 15 22 10 15 8 8 33 1.4 59 14 18 17 8 8 8 8 34 1.5 43
12 17 10 6 10 5-6 4 35 0.97 49 21 13 10 11 20 8 8 36 0.85 38 22 12
18 12 20 8 8 Comp. 1.2 39 17 14 28 7 Resolved at 15 .mu.m. The film
1 or -- Ex. 4 thickness after development less reduced to 12 .mu.m.
Residual is slightly attached to the unirradiated part in the form
of sponge. Comp. 2.1 70 12 -- -- -- A clear 20 .mu.m line/space 5-6
4 Ex. 5 pattern is not obtained because a cross-section of the line
showed an inverse trapezoid having a sharp inclination. Comp. 0.73
49 27 16 14 11 Resolved at 40 .mu.m. The 30 1 or -- Ex. 6 .mu.m
line was swelled. The film less thickness after development reduced
to 19 .mu.m. Residual is slightly attached to the unirradiated part
in the form of sponge.
__________________________________________________________________________
TABLE 13
__________________________________________________________________________
Polyimide film Water Photosensitive composition Exposure Tensile
Line/space Pull resistance Polyimide Coating Viscosity Thickness
energy Strength Elongation Thickness resolution test test Ex.
precursor absorbance (poise) (.mu.m) (mJ/cm.sup.2) (kg/mm.sup.2)
(%) (.mu.m) (.mu.m) (kg/mm.sup.2) (kg/mm.sup.2)
__________________________________________________________________________
37 W-37 A1-26 1.3 56 13 600 *.sup.1 15 16 7 10 8 8 38 W-38 A1-28
1.2 42 13 700 *.sup.2 15 14 7 10 8 8 39 W-39 A1-29 1.4 40 13 600
*.sup.2 14 12 7 15 8 8 40 W-40 A1-30 1.5 52 13 500 *.sup.2 15 16 7
15 8 8 41 W-41 A4- 2 1.5 30 13 500 *.sup.1 15 25 7 20 8 8 42 W-42
A4- 3 1.1 28 13 500 *.sup.1 16 20 7 20 8 8 43 W-43 A3-11 1.1 33 13
500 *.sup.1 15 20 7 10 8 8 44 W-44 A3-12 1.1 35 13 600 *.sup.1 15
14 7 10 8 8 45 W-45 A3-13 1.1 39 13 500 *.sup.1 14 21 7 10 8 8
__________________________________________________________________________
*.sup.1 : iline stepper FPA 2001 iI (manufactured by Canon Inc.)
*.sup.2 : iline NSR1505 i7A (manufactured by Nikon Corporation)
TABLE 14
__________________________________________________________________________
Photosensitive composition Polyimide film Water N-methyl Tensile
Line/space Pull resistance Polyimide pyrrolidone Coating Viscosity
Thickness strength Elongation Thickness resolution test test Ex.
precursor (g) absorbance (poise) (.mu.m) (kg/mm.sup.2) (%) (.mu.m)
(.mu.m) (kg/mm.sup.2) (kg/mm.sup.2)
__________________________________________________________________________
47 W-47 A1-32 80 0.9 41 24 15 30 12 20 5-6 3 or less 48 W-48 A1-33
70 1.4 49 13 20 14 7 15 5-6 3 or less 50 W-50 A1-35 70 0.6 39 24 14
35 12 20 5-6 3 or less 51 W-51 A1-36 80 0.9 34 16 14 85 9 20 8
__________________________________________________________________________
8
TABLE 15
__________________________________________________________________________
Photosensitive composition Polyimide film Water Tensile Line/space
Pull resistance Polyimide Coating Viscosity Thickness Strength
Elongation Thickness resolution test test Ex. precursor absorbance
(poise) (.mu.m) (kg/mm.sup.2) (%) (.mu.m) (.mu.m) (kg/mm.sup.2)
(kg/mm.sup.2)
__________________________________________________________________________
53 W-53 A5-5 0.5 68 25 14 20 13 25 8 8 54 W-54 A5-6 1.1 73 18 14 30
10 20 8 8
__________________________________________________________________________
TABLE 16 ______________________________________ Heat resistance
Thermal stability Long of polyimide film Ex. of composition
development (i) (ii) ______________________________________ 1 5% or
less .smallcircle. .smallcircle. .smallcircle. 2 +20% .DELTA.
.smallcircle. .DELTA. 3 N.D. x .DELTA. .smallcircle. 4 -15% .DELTA.
.smallcircle. .DELTA. 5 5% or less .smallcircle. .smallcircle.
.smallcircle. 6 5% or less .smallcircle. .smallcircle.
.smallcircle. 7 5% or less .smallcircle. .smallcircle.
.smallcircle. 8 5% or less .smallcircle. .smallcircle.
.smallcircle. 9 5% or less .smallcircle. .smallcircle.
.smallcircle. 10 5% or less .smallcircle. .smallcircle.
.smallcircle. 11 5% or less .smallcircle. .DELTA. .DELTA. 12 5% or
less .smallcircle. .smallcircle. .smallcircle. 13 5% or less
.smallcircle. .smallcircle. .smallcircle. 14 5% or less
.smallcircle. .smallcircle. .smallcircle. 15 5% or less
.smallcircle. .smallcircle. .smallcircle. 16 5% or less
.smallcircle. .smallcircle. .DELTA. 17 5% or less .smallcircle.
.smallcircle. .DELTA. 18 5% or less .smallcircle. .DELTA. .DELTA.
19 N.D. x .smallcircle. .smallcircle. 20 N.D. x .smallcircle.
.smallcircle. 21 N.D. x .smallcircle. .smallcircle. 22 N.D. x
.smallcircle. .smallcircle. 23 N.D. x .smallcircle. .smallcircle.
24 N.D. x .smallcircle. .smallcircle. 25 N.D. x .smallcircle.
.smallcircle. ______________________________________
TABLE 17 ______________________________________ Heat resistance
Thermal stability Long of polyimide film Ex. of composition
development (i) (ii) ______________________________________ 26 N.D.
x .smallcircle. .smallcircle. 27 5% or less .smallcircle.
.smallcircle. .smallcircle. 28 5% or less .smallcircle.
.smallcircle. .DELTA. 29 5% or less .smallcircle. -- -- 30 +25%
.DELTA. -- -- 31 N.D. x -- -- 32 5% or less .smallcircle. -- -- 33
5% or less .smallcircle. -- -- 34 5% or less .smallcircle. -- -- 35
5% or less .smallcircle. -- -- 36 5% or less .smallcircle. -- -- 37
5% or less .smallcircle. -- -- 38 5% or less .smallcircle. -- -- 39
5% or less .smallcircle. .smallcircle. .DELTA. 40 5% or less
.smallcircle. -- -- 41 -20% .DELTA. -- -- 42 -15% .DELTA.
.smallcircle. .DELTA. 43 N.D. x -- -- 44 N.D. x -- -- 45 N.D. x --
-- 46 5% or less .smallcircle. -- -- 47 5% or less .smallcircle. --
-- 48 5% or less .smallcircle. -- -- 49 5% or less .smallcircle. --
-- 50 5% or less .smallcircle. -- --
______________________________________
TABLE 18 ______________________________________ Heat resistance
Thermal stability Long of polyimide film Ex. of composition
development (i) (ii) ______________________________________ 51 5%
or less .smallcircle. .smallcircle. .DELTA. 52 5% or less
.smallcircle. -- -- 53 5% or less .smallcircle. .smallcircle.
.DELTA. 54 5% or less .smallcircle. .smallcircle. .DELTA. Comp. 5%
or less -- -- -- Ex. 1 Comp. 5% or less -- -- -- Ex. 2 Comp. 5% or
less -- x x Ex. 3 Comp. 5% or less x*.sup.1 -- -- Ex. 4 Comp. 5% or
less -- -- -- Ex. 5 Comp. 5% or less x*.sup.2 -- -- Ex. 6 Comp. 5%
or less -- -- -- Ex. 7 ______________________________________
*.sup.1 : The film thickness reduced to 9 mm. *.sup.2 : The films
thickness reduced to 15 mm. --: Not measured.
* * * * *